Rev Chem Eng 2015; 31(4): 361–381

Pranav D. Pathak, Sachin A. Mandavgane* and Bhaskar D. Kulkarni

Fruit peel waste as a novel low-cost bio adsorbent

DOI 10.1515/revce-2014-0041 BNP Breadnut peel
Received September 17, 2014; accepted May 22, 2015; previously BOD Biological oxygen demand
published online July 10, 2015 BP Banana peel
BS Banana stalk
CAP Cassava peel
Abstract: Fruit peel waste (FPW) is abundantly available
CFP Cactus fruit peel
from the agricultural and food processing industry and
Co Initial concentration (mg/l)
has been studied in recent past as an adsorbent. This
COD Chemical oxygen demand
paper critically reviews the reported work and investi-
CP Citrus peel
gates various FPW-pollutant systems. The study includes
CSP Cucumis sativa peel
statistics of FPW generation, modification, characteriza-
CTP Carrot peel
tion, adsorption ability, recovery/regeneration, and mod-
CUP Cucumber peel
eling (isotherms, kinetics, and thermodynamics) of batch
Di Column diameter
adsorption. It is found that orange and banana peels are
DP Durian peel
the most extensively studied adsorbents, whereas Pb2+ and
FPW Fruit peel waste
methylene blue are the most efficiently removed pollut-
GFP Grapefruit peel
ants, the Langmuir and Freundlich adsorption isotherms
GP Garlic peel
provide the best fit in most of the cases, and in general,
GPP Green Pea peels
pseudo-second-order kinetics is followed. There are very
GUP Guava peel
limited column studies and no report on commercial plant.
H Column depth
Though the reproducibility of the results is poor, FPW has a
JFP Jackfruit peel
great potential in the wastewater treatment due to its abun-
KP Kohlrabi peel
dant and cheap availability. FPW can be used for removal
LP Lemon peel
of heavy metals and dyes; however, removal of organic and
LPP Litchi pericarp
gaseous impurities needs further investigation.
MB Methylene blue
MG Malachite green
Keywords: adsorbent; adsorption; fruit peel waste;
MMP Muskmelon peel/melon peel
organic and inorganic pollutants; wastewater.
MP Mango peel
MSP Mangosteen peel
OC & PE Organic compounds and pesticides
Abbreviations ONP Onion peel
OP Orange peel
% Rec % Recovery PAP Pineapple peel
AMP Amla (gooseberry fruit) peel PMP Ponkan mandarin peel
AP Apple peel POP Ponkan peel
BBP Broad bean peels PP Pomegranate peel
BGP Bitter gourd peel PTP Potato peel
PUP Pummelo peel/pomelo peel
*Corresponding author: Sachin A. Mandavgane, Visvesvaraya PYP Papaya peel
National Institute of Technology, Department of Chemical Qm Langmuir adsorption capacity (mg/g)
Engineering, South Ambazari Road, Nagpur, Maharashtra 440010, RB Rhodamine B
India, e-mail: sam@che.vnit.ac.in RP Rambutan peel
Pranav D. Pathak: Visvesvaraya National Institute of Technology,
RT Room temperature
Department of Chemical Engineering, South Ambazari Road,
Nagpur, Maharashtra 440010, India
SCFP Schizandrachinesis fruit peel
Bhaskar D. Kulkarni: CSIR-National Chemical Laboratory, T Temperature (°C)
Pune 411008, India t Time (min)

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362 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent

t∞ Column saturation time (min) agriculture industries is a serious environmental concern.

TFP Tea fruit peel India is the second largest producer and consumer of fruits,
YPFP Yellow passion fruit peel which is also an indication of the generation of million
ZP Zalaccaedulis peel tons of fruit waste per year (Sharma et al. 2011, Patel 2012).
Such fruit waste can be effectively used for effluent
treatment. Potential advantages of use of fruit waste as
a low-cost biosorbent are (1) abundant availability, (2)
1 Introduction low cost, (3) good adsorption capacity, (4) easy-to-make
chemical modification, (5) easy regeneration and (6) less
Safe drinking water is necessary for every living o ­ rganism disposal problem after adsorption.
on earth. It is known that from among the total amount
of water, only 2.5% is fresh water and 98.8% of that water
is either groundwater or is in the form of ice. Of this 2 Global fruit production scenario
small amount of freshwater, < 0.3% is in lakes, rivers,
and atmosphere and provides the useable sources. Water Country-wise fruit production is listed in Table 1. India is
plays a vital role in the world economy. It is widely used the second largest producer of fruits after China (20.39%),
in agriculture and in industry as a solvent and helps for with a world production contribution of 12.49%. Brazil
transportation and cooling. is third and USA is fourth (Table 1; source: Indian Horti-
The rapid and continuous growth of industries over culture Database–2011, 2011; Ministry of Commerce and
the last few decades has increased fresh water demand Industry Govt. of India., http://agriexchange.apeda.
and, as a consequence, also the amount of wastewater gov.in) http://www.data.gov.in/dataset/all-india-and-
discharged. This wastewater contains many organic and state-wise-area-andproduction-fruits.
inorganic matters, in the form of heavy metals, aromatic
compounds, dyes, pigments, etc. Many of them have
Table 1: Major fruit-producing countries in the world (2010–2011).
been classified as hazardous pollutants because of their
potential toxicity to human health. A number of methods Sr. Country Production Contribution
are available for the removal of pollutants from aqueous No. in MT (%)
solution. These methods include chemical precipitation,
1. China 122,184,944 20.39
ion exchange, membrane separation process, biological 2. India 74,878,000 12.49
degradation, chemical oxidation, solvent extraction, and 3. Brazil 39,286,781 6.56
adsorption (Yıldız et al. 2005, Yan et al. 2007). 4. United States of America 25,383,917 4.24
Among all these methods, adsorption is the most 5. Italy 16,907,895 2.82
popular since it is a very simple technique due to its con- 6. Philippines 16,181,731 2.70
venience, ease of operation, and versatility. This process 7. Mexico 15,255,598 2.55
8. Spain 15,184,420 2.53
can minimize or remove different types of pollutants and
9. Indonesia 14,867,762 2.48
is thus having a wide range of applications in wastewater 10. Turkey 13,945,604 2.33
treatment (Robinson et al. 2002, Mittal et al. 2007). 11. Others 245,223,757 40.92
Activated carbon is a commonly used adsorbent for World total 599,300,409
removal of various pollutants from wastewater; however,
its use is limited due to its high cost. Recently, a number of
nonconventional adsorbents have been used due to their
capability to remove different pollutants from wastewater
(Bhatnagar et al. 2010b).
Nonconventional adsorbents are classified into five
different categories: (1) waste materials from agriculture
and industry, (2) fruit waste, (3) plant waste, (4) natural
inorganic materials, and (5) bioadsorbents (living and
nonliving biomass) (Sharma et al. 2011).
This article reviews use of fruit peel waste (FPW) for
the removal of different pollutants from wastewater. FPW
produced in large quantities from food processing and Figure 1: FPW generation (see Wadhwa and Bakshi 2013/2014).

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 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
Figure 1 presents country-wise fruit and vegeta-
ble waste generation data. India is fourth in generation
of fruit and vegetable waste after china, USA, and the
Philippines. Annually, India generates approximately
­ Water pollution due to discharge of dyes from textile,
about 1.81 million tons of waste from fruit and vegeta-
ble processing industries. In addition, China, the USA,
and the Philippines generate about 31.98, 14.95, and
6.53 million tons, respectively, of fruit and vegetable waste
every year. This suggests a huge availability of fruit and
vegetable wastes for the posttreatment processes (use it
for adsorption, gasification, or some other).
These wastes are either composted or dumped in
landfills/rivers, causing pollution and foul smell. Some
alternative disposal methods may possibly recycle this
complete material as feed resources for cattle or pigs and/
or further processing to extract or develop some value-
added products. Furthermore, contributing to sustainable
intensification of livestock industry will convert “wastes
to opportunities for development” (Tartrakoon et al. 1999,
Wadhwa and Bakshi 2013/2014).
3 Pollutants adsorbed on FPW
Wastewater contains different pollutants such as organic
and inorganic compounds, heavy metals, and dyes. These
pollutants are sometimes present in trace amount but may
cause a serious human health problem. Generally, organic
pollutants present in wastewater increase biological oxygen
demand (BOD) and chemical oxygen demand (COD) and
eventually lead to depletion of oxygen content in water. It
results in hypertrophication, which threatens aquatic life.
Organic pollutants in wastewater are mainly organic
acids such as carboxylic and sulfonic acids and phenolic
compounds and have good solubility in water with poor
biodegradation properties (Pan et al. 2002). Phenols, due
to their toxicity and possible accumulation in the environ-
ment, are considered persistent pollutant. Phenol contents
in drinking water as per World Health Organization recom-
mendation should not exceed 0.001 mg/l. The biological
degradation of phenol occurs very slowly or does not occur
at all (Bhatnagar and Minocha 2009, Lin and Juang 2009).
Due to nondegradability and toxicity to large variety
of living organisms even at very low concentration, heavy
metal pollutants are considered as serious environmental
issues (El-Ashtoukhy et al. 2008, Khosravan and Lashkari
2011). Metals like Pb, Cr, Hg, U, Se, Zn, As, Cd, Co, Cu, and
Ni are classified as toxic (Johnson et al. 2008). Industries
like mining, automotive, metal finishing, metal painting,
aerospace, alloys, paints, batteries, preservatives, and
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363
pesticides are the major sources for metal ion discharge
into wastewater (Rubio and Tessele 1997, Das et al. 2008,
El-Ashtoukhy et al. 2008).
paper, cosmetics, and food is one other major environ-
mental concern. Dyes are highly visible even at very trace
concentrations due to their coloring properties and cause
aesthetic and ecological problems to the aquatic ecosys-
tem (Kannan and Sundaram 2001, Robinson et al. 2002,
Mittal et al. 2007). Other types of water contaminants are
pesticides (Fushiwaki and Uranob 2001), fines, oils, and
others (Rubio and Tessele 1997).
Some other organic pollutants such as palm oil mill
effluent (Mohammed and Chong 2014), pesticides (Silva
et al. 2013), some phenolic compounds (Agarry et al. 2013,
Edison and Sethuraman 2013), and inorganic pollutants
like oil/grease particles (El-Nafaty et al. 2013, Borhan et al.
2014), lubricating oil, and diesel (Zou et al. 2014) have
been removed by using FPW.
For the removal of these pollutants from wastewaters,
different naturally available and/or synthetic resins and
nonconventional adsorbents are used. A ­ hmaruzzaman
(2008) reviewed the adsorption of phenolic compounds
on low-cost adsorbents, which include some natural
materials, bioadsorbents, and waste materials/byprod-
ucts from agriculture and industry. Lin and Juang (2009)
also reviewed the adsorption of phenol and its derivatives
from water using synthetic resins and low-cost natural
adsorbents. Aksu (2005) studied the use of different
microorganisms for the removal of organic pollutants.
Sud et al. (2008) gives detailed ideas about adsorption of
heavy metal on agricultural wastes. The applicability of
some naturally available adsorbents for the removal of
dyes from aqueous waste was reviewed by Sharma et al.
(2011).
Different authors have reviewed waste and naturally
occurring low-cost materials like siliceous materials,
clay, zeolite, chitin, chitosan, activated carbon produced
from solid wastes, biomass, and industrial and agri-
cultural byproducts/waste materials as an adsorbent.
This paper attempts to review FPW as an adsorbent for
removal of heavy metals, dyes, organic, and inorganic
pollutants.
Supplemental Table S1 gives a bird’s eye view of dif-
ferent FPW-pollutant systems studied. From the table, it
can be concluded that metal pollutants Pb2+, Cu2+, Cd2+,
and dye methylene blue (MB) were effectively removed
by FPW. Orange peel (OP), banana peel (BP), pomegran-
ate peel (PP), and garlic peel (GP) were effectively used
for removal of pollutants (metal, dyes, and organic
­pollutants) from wastewater.
364 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent

Table 2: Analytical techniques used in the characterization of FPW.

Analytical method Application References

IR or FTIR Determine active sites and active groups present on the Marín et al. 2010, Ay et al. 2012, Gupta and
surface of the FPW Nayak 2012
SEM Visual validation of surface morphology of the FPW Memon et al. 2008b, Ning-Chuan et al. 2010,
Gupta and Nayak 2012
EDS Element analysis and chemical characterization of metal Lugo-Lugo et al. 2012
bound on the FPW
XRF For elemental analysis of FPW Lim et al. 2014
XRD Crystallographic structure and chemical composition of Gupta and Nayak 2012
the FPW
C NMR
13
Determine the active sites of the FPW Marín et al. 2010
TGA Describe the thermal stability of the FPW Ay et al. 2012
CHNS Determines the percentage carbon, hydrogen, nitrogen, Lim et al. 2014
and sulfur present in the FPW
BET surface area and Determines the surface area, porosity, and pore volume Ay et al. 2012, Gupta and Nayak 2012
pore volume of the FPW
pHpzc Determines the surface charges on the FPW surface Ay et al. 2012, Gupta and Nayak 2012
Proximate analysis Determines moisture, ash, dry matter, fix carbon content Memon et al. 2008b
in the FPW
EDX Used for the determination of the elemental composition Memon et al. 2008b and Memon et al. 2009
of FPW
TEM Capable of imaging at a significantly higher resolution Gupta and Nayak 2012
then SEM
VSM Used for the determination of magnetic properties of FPW Gupta and Nayak 2012
Fats, fiber, and protein Determines the fats, fiber, and protein content of FPW Lim et al. 2014

4 C
 haracterization and analytical
methods used for FPW
FPW was characterized to understand surface morphology
and physico-chemical properties by using sophisticated
analytical tools like infrared absorption spectroscopy or
Fourier transformed infrared spectroscopy (IR or FTIR),
scanning electron microscopy (SEM), energy dispersive X-ray
(EDS), x-ray fluorescence (XRF), X-ray diffraction (XRD),
nuclear magnetic resonance (NMR), thermogravimetric
analysis (TGA), Brunauer-Emmett-Teller (BET) surface area,
elemental analysis, point of zero charge (pHpzc), proximate
analysis, energy-dispersive X-ray spectroscopy (EDX), trans-
mission electron microscopy (TEM), and vibrating sample
magnetometer (VSM) of FPW (Memon et al. 2009, Marín
et al. 2010, Ning-Chuan et al. 2010, Ay et al. 2012, Gupta and
Nayak 2012, Lugo-Lugo et al. 2012, Lim et al. 2014). Table 2
summarizes the information that can be revealed by each of
the analytical/ instrumental method listed.
Agricultural waste has basic chemical constituents
like cellulose, hemicellulose, lignin, lipids, proteins,
sugars, starch, polysaccharides, and pigments. These
constituents contain different functional groups such as
carboxyl, hydroxyl, sulfhydryl, and amino. These groups
are present on their surfaces and have ability to bind the
sorbate ions and molecules (Qin et al. 2012, Huang and
Zhu 2013, Meisam et al. 2013).
Among these analytical methods, determination of
pHpzc is very important. To understand the adsorption
mechanism, it is essential to determine the pHpzc of the
adsorbent. Adsorption of cations is favored at pH > pHpzc,
while the adsorption of anions is favored at pH < pHpzc
(Srivastava et al. 2006). The pHpzc for some FPW is com-
piled in Table 3.
Surface area is one of the key factors for adsorption.
Adsorption is directly proportional to the surface area.
FPW surface is porous and may contain micro pores, mes-
opores, and/or macro pores. Along with area, pore volume
and pore diameter are also influencing factors. Pore volume
and pore diameter determine the degree or extent of dif-
fusion of pollutant molecules into the pores. Depending
upon the size of the molecule and pore diameter, pore dif-
fusion can be estimated. If the diameter of the pore is larger
than the diameter of the adsorbate molecule, then the mol-
ecule diffuses deeper into the pore. Table 4 gives an order
of magnitude of BET surface area of some FPWs. Compared
with activated carbon and siliceous materials, the surface
area of peels is very low, and this is a self-­characteristic of
carbonaceous materials (Castro et al. 2011).

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 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent 365

Table 3: pHpzc and active sites present on the surface of fruit and vegetable peels.

Peel pHpzc References

AMP 6 Rao and Ikram 2011

OP 3.9 Nascimento et al. 2014a,b
BP 2.41 Palma et al. 2011
PP 2.35 Ay et al. 2012
MP 4.4 Iqbal et al. 2009
CSP 4.0 Thirumalisamy and Subbin 2010
ZP 4.8 Sirilamduan et al. 2011
LP 4.65 Thirumavalavan et al. 2010
PP 6.53 Güzel et al. 2012
BNP 4.8 Lim et al. 2014
ASP 4.8 Sreenivas et al. 2014
CFP (C. hildmannianus species) 4.54 Gilioli et al. 2013
PTP 6.59 Mutongo et al. 2014
GP 4.25–4.45 Chowdhury et al. 2012
ONP 4.55–4.75

Table 4: BET surface area and pore volume of FPW. involves cleaning, drying, and thermal treatment of FPW.
Chemical treatment is used to influence/alter properties
Peel BET surface References like water sorbency, ion exchange capability, conductivity,
area (m2/g)
hydrophilicity, or hydrophobicity of cellulosic materials. The
OP 1.999 Thirumavalavan et al. 2011 chemical treatment methods include protonation, xanthan-
OP 47.03 Gupta and Nayak 2012 ation, chemical pyrolysis, saponification, halogenation, oxi-
OP 22.4 Hashemian et al. 2013
dation, polymerization and removal of inhibiting groups (the
OP 2.14 Nascimento et al. 2014a
OP 15.8 Nascimento et al. 2014b groups on the surface that inhibit adsorption of the selected
BP 1.272 Thirumavalavan et al. 2011 moieties), deamination, and decarboxylation. Some other
BP 13 Memon et al. 2008a, 2009 treatment involves the use of supercritical CO2 for enhancing
BP 32.3 Agarry et al. 2013 the significant charges on lignocellulosic tissues. Figure 2
BP 1.67 Liu et al. 2013
shows process pathways to treat/modify/alter raw FPW
LP 1.271 Thirumavalavan et al. 2011
PP 10 Ay et al. 2012
material by which the effective and durable and repeated
CAP 3.72 Alfin et al. 2011 long-term application can be made. The detailed modifica-
POP 115.3 Pavana et al. 2008 tion or treatment methods are listed in Table 5.
PAP 1.99 Foo et al. 2011 For the maximum adsorption of pollutants, it is neces-
GUP 3.04 Foo et al. 2011 sary that an appropriate activation process is selected. Out
PMP 119.3 Pavan et al. 2006
of listed treatments, physical treatments are simple and
SCFP 445 Koduru et al. 2013
inexpensive. However, they are less effective than chemical
modifications. Generally, acid washing increases cationic or
basic pollutant adsorption. Some treatment methods such
5 Treatment of FPW as physical or chemical carbonization can cause weight loss
of the biosorbent. Pretreatment is a very easy process among
The use of raw FPW as an adsorbent can give rise to prob- the other chemical processes. To enhance adsorption capac-
lems such as (1) low adsorption capacity, (2) high COD, (3) ity of FPW, most of the researchers prefer only washing with
high BOD, and (4) high total organic carbon (TOC) due to acid, alkali, or some other solvent (Gaballah et al. 1994,
leaching of soluble organic compounds present in the FPW. Ngah and Hanafia 2008, O’Connell et al. 2008, Park et al.
The increase of COD, BOD, and TOC leads to hyper- 2010, Patel 2012). Detailed physical and chemical treatment
trophication. So, FPW needs to be treated or modified methods used for FPW are listed in Supplemental Table S2.
before use. The treatment of FPW can alter its physical and Researchers have tried different physical and chemi-
chemical properties, along with its adsorption ­capacity. Dif- cal modification treatments for improving the adsorption
ferent physical, chemical, and other treatment or modifica- capacity of FPW. It is worth noting that uptake capacity of
tion methods are listed in the literature. Physical treatment same pollutant-FPW system reported by different workers is

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366 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent

obtained 4 times higher adsorption capacity compared

Figure 2: Schematic diagram for processing different types of
native FPW.
substantially different. For example, the adsorption capac-
ity of Pb2+ on untreated OP reported by Feng et al. (2011),
Thirumavalavan et al. (2011), and Liang et al. (2009a) is
135.5 mg/g, 27.10 mg/g, and 89.77 mg/g, respectively.
Feng et al. (2009, 2011) extensively studied OP grafted
with polyacrylic acid and achieved higher adsorption
capacity compared with untreated OP. The adsorption
capacity for Pb2+, Cd2+, Cu2+, and Ni2+ is 4.2, 4.6, 6.5, and
16.55 times higher than untreated OP.
Thirumavalavan et al. (2011) used cellulose extracted
OP and BP for adsorption of different metal ions. They
with untreated FPW. The adsorption capacity for Cu2+, Pb2+,
Zn2+, Ni2+, and Cd2+ was increased by 4,4.2, 4.4, 2.4, and 2.5
times, respectively, for cellulose extracted OP, while it was
found 2.7, 3.9, 4.7, 2.5, and 2.4 times increased for cellulose
extracted BP. Thus, on both cellulose extracted peels,
increase in the uptake capacity for each metal ion was
observed and magnitudes were comparable.
Chemical modification by soaking in acid (HCl, H2SO4,
HNO3, and H3PO4), base (NaOH, KOH, Na2CO3), or physi-
cal modification by carbonation was found to increase
adsorption capacity by 1.5–2.5 times compared with
untreated FPW. Thus, polyacrylic acid grafted and cel-
lulose extracted FPWs are more efficient for metal ion
removal.
In case of dye adsorption, chemical modification with
acids (HCl, H2SO4 and H3PO4) or base (NaOH) and carboni-
zation at 400–600°C in N2 environment increase adsorp-
tion capacity by 2–3 times compared with raw peels.
For removing organic pollutants, carbonization at
500–700°C and under inert medium is more effective.
6 Factors affecting adsorption
Adsorption is affected by operational parameters, surface
properties of the adsorbent, and chemical nature of the
adsorbate.

Table 5: Modification or treatment methods for converting raw biomass into improved adsorbents.

Type of Steps involved in treatment Details of treatment

treatment

Physical modification
Chemical modification
Pretreatment (washing)
Binding group enhancement
Blocking or elimination of
functional group
Polymer grafting
Other compound loading
Microwave activation
Sun or oven drying, cutting, grinding, sieving, thermal pyrolysis, autoclaving, steam, etc.
Alkales: NaOH, KOH, Ca(OH)2, NH4OH, etc.
Acids: H2SO4, HCL, HNO3, H3PO4, citric acid, acetic acid, etc.
Organic solvents: methanol, ethanol, isopropyl alcohol, formaldehyde, acetone, EDTA,
toluene, carbon disulfide, carbon tetra chloride, etc.
Other chemicals: MgCl2, ZnCl2, K2CO3, etc.
Carboxylation of hydroxyl group, amination of hydroxyl group, phosphorylation
of hydroxyl group, carboxylation of amine group, saponification, xanthanation,
halogenation, oxidation, extraction of cellulose, etc.
Deamination or elimination of amine group, decarboxylation or elimination of carboxylic
group, etc.
Poly-acrylamide-cometacralic acid, formaldehyde, polyacrylic acid, polyvinyl alcohol,
polyvinyl pyrrolidone (K25) crosslinking with CS2, etc.
Fe3O4, Fe or Fe nanoparticle, Zirconium, Pluronic F127, etc.
NaOH, K2CO3, etc.

Detail surface modification methods and their references are given in the Supplemental Table S2.

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 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
6.1 Operational parameters
Adsorption on FPW depends on different parameters. The
major factors affecting adsorption process are (1) adsor-
bent dose, (2) contact time, (3) solution pH, (4) initial
adsorbate concentration, (5) temperature, (6) particle size
of the FPW, and (7) speed of agitation.
The amount of adsorbent decides the extent of avail-
able surface binding sites for adsorption. Hence, the per-
centage removal of adsorbate increases with adsorbent
dosage. After reaching equilibrium, no further change
in the percentage removal of the adsorbate can occur.
This indicates that when the optimum solid/liquid ratio
is used, the amount of adsorbent is sufficient for the
maximum removal of adsorbate ions from the solution at
a given concentration. Even if more adsorbent is used, it
does not affect removal.
Contact time is the time required for the system to
reach equilibrium. This solid/liquid heterogeneous system
frequently undergoes different mass transfer steps, some
of which could be comparatively slow. Therefore, it is nec-
essary to determine the contact time to make sure that the
equilibrium is reached.
pH is considered to be the most important parameter
in the adsorption process. It affects the solution chemis-
try, functional group activity on the FPW surface, and the
composition of the adsorbate. As the pH varies from acidic
to basic, it enhances adsorptive removal of basic dyes or
cationic metals.
The initial concentration of the adsorbate provides
a necessary driving force to overcome the mass transfer
resistance between the adsorbate in the bulk phase and
FPW. Higher initial concentrations give higher loading
capacity.
Rate of adsorption increases with temperature, as
higher temperature enhances the mobility of adsorbate
ions and decreases the viscosity of the solution. A temper-
ature study also helps in understanding thermodynamic
parameters such as enthalpy, entropy, and free energy
involved in the adsorption process.
Surface area increases with a decrease in particle
size. A higher surface area gives more number of binding
sites for adsorption. Small particle size lowers the mass
transfer driving force per unit area of adsorbent particles,
which increases the uptake/saturation capacity per unit
mass of FPW.
Agitation speed helps the adsorbate overcome the
boundary layer mass transfer resistance. Higher agitation
speed results in higher rate of adsorption (Marín et al. 2010,
Mishra et al. 2010, Dod et al. 2012, Huang and Zhu 2013,
Lim et al. 2014).
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367
6.2 Properties of FPW
Adsorption is affected by the physico-chemical and
surface properties of the adsorbent, like elemental compo-
sition, porosity, particle density, bulk density, surface pH,
surface area, functional groups present on the surface,
and thermal properties.
6.3 Chemical nature of an adsorbate
Section 3 discussed the different adsorbates reportedly
adsorbed on FPW. Factors like charges on adsorbate, size
of moiety, functional groups, solubility, hydrophobicity/
hydrophilicity, reactivity, relative affinity between the
solution and the adsorbent, thermodynamics of the solu-
tion, and, in case of organic pollutants, dissociation con-
stant also affect adsorption (Fomina and Gadd 2014).
7 Adsorption kinetics
Adsorption kinetics study is useful for the design of an
adsorption system. It provides important information
about the rate of adsorption and adsorption mechanism.
The adsorption process may involve different transport
stages. Adsorption kinetics is one of the important factors
that explain the effectiveness of an adsorbent. It defines
the rate of adsorbate uptake, which physically controls
the diffusion process. Residence time of adsorbate uptake
at the solid-solution interface is also explained by the
kinetics. Adsorption kinetics is controlled by different
independent processes acting in series or in parallel.
These processes are bulk diffusion, external mass transfer
(film diffusion), intraparticle diffusion, and chemisorp-
tion (chemical reaction) (Behnamfard and Salarirad 2009,
Ijagbemi et al. 2010).
A wide variety of adsorption kinetic models has
been employed to understand FPW adsorption system.
The kinetic models like pseudo-first-order, first-order
reversible, pseudo-second-order, Ritchie second-order,
­
modified Ritchie second-order, Elovich, Reichenberg,
and Weber-Morris intraparticle diffusion models have
been formulated and used for adsorption of different
adsorbents on FPW.
Though various kinetic models were applied by
different researchers to FPW batch adsorption data,
the pseudo-first-order, pseudo-second-order, Elovich,
and Weber-Morris intraparticle diffusion models were
applied to most of the systems. Out of these models,
368 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
pseudo-­second-order fits better than other models do.
In none of the systems, Weber-Morris intraparticle dif-
fusion model curve is a straight line passing through
origin, which confirms that diffusion is not the only rate-
controlling step and more than one factor affects adsorp-
tion on FPW.
8 A
 dsorption isotherm and
modeling
Generally, adsorption isotherm is a curve that gives infor-
mation about the amount of adsorbate removed from the
aqueous solution at equilibrium state per unit mass of
adsorbate at constant temperature and pH. Adsorption
equilibrium provides important physico-chemical data
for evaluating the applicability of adsorption process as
a unit operation. Adsorption equilibrium is the ratio of
adsorbed amount of adsorbate to the remaining amount
of adsorbate in the solution. The equilibrium is estab-
lished when the adsorbate solution and adsorbent come
into contact for a sufficient time. At equilibrium, the
sorbate concentration in the bulk solution and that at
interface are in dynamic balance. The most important
step to optimize and design an adsorption process as well
as the adsorbate and adsorbent is prediction of a suit-
able isotherm for representing the equilibrium state of an
adsorption system. The physico-chemical parameters of
different isotherms, together with the fundamental ther-
modynamic assumptions, help to understand the adsorp-
tion mechanism, the surface properties of the adsorbate,
and the degree of affinity (Ho et al. 2002, Behnamfard
and Salarirad 2009, Foo and Hameed 2010; Tümsek and
Avcı 2013).
FPW batch adsorption data for different systems have
been fitted to a wide variety of equilibrium isotherms, like
Langmuir, Freundlich, Sips, Redliche-Peterson, Temkin,
Dubinin-Raduskevich, Dubinine-Kaganere-Radushkevich,
Toth, Koble-Corrigan, Harkins-Jura, Flory-Huggins, ion
exchange, generalized isotherm, Langmuir-Hinshelwood,
and BET, and used for modeling FPW-adsorption systems
data (Perez-Marın et al. 2007, Khaled et al. 2009a, Marín
et al. 2009, Khaskheli et al. 2011, Foo and Hameed 2012,
Zou et al. 2012).
Though various isotherm models were applied by
different researchers to FPW batch adsorption data, the
Langmuir and Freundlich models were most commonly
applied in most of the systems. Out of these two models,
Langmuir fits better than Freundlich does, which suggests
that adsorption on FPW is most often monolayered.
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9 B
 atch adsorption studies using
FPW
Wide varieties of FPWs were used for removal of different
organic and inorganic compounds (dyes, heavy materi-
als, phenolic compounds, pesticides, etc.). In general,
FPW shows good adsorption capacity toward different
pollutants. FPWs have appropriate characteristics and
structural properties to adsorb organic and inorganic ions
(especially metal and dye ion) on binding sites present
on their surfaces by their interactions with the chemical
functional groups.
The maximum adsorption capacity, along with
surface activation process and actual experimental condi-
tions (e.g. pH, initial concentration, temperature, contact
time, particle size), for adsorptive removal of pollutants
is summarized in Supplemental Table S2 (supplementary
information), and the comparison of different FPW for a
particular pollutant is tabulated in Supplemental Table S3
(supplementary information), and several of the results
are discussed hereinafter. Table 6 gives some representa-
tive collection of batch adsorptive studies. Due to different
operating conditions, materials, and methodologies, it is
difficult to conclude the suitability of a particular FPW as
an adsorbent of choice.
Figure 3 shows the comparison of different FPWs for
their use for the adsorption of heavy metal, dyes, organic
compounds, or some other pollutants. From the figure,
it is clear that OP and BP are the most utilized materials
for the removal of pollutants due to their wide availability
all over the world. OP specifically shows good adsorption
capacity toward metal ions and dyes as compared to other
citrus family (citrus peel [CP], lemon peel [LP], ponkan
mandarin peel [PMP], pummelo peel/pomelo peel [PUP],
and POM). BP, on the other hand, is the only versatile peel
that can be utilized for wide variety of pollutants such as
dyes, heavy metal, organic (waste effluent from indus-
tries), and inorganic (diesel/lubricating oil/grease parti-
cles) pollutants. BP has some basic character (Palma et al.
2011) due to which it can adsorb cations as well as anions.
Researchers have reported a wide range of FPW as
an adsorbent. The aim behind this may be to use locally
available FPW to solve the dual issue. First is the utiliza-
tion of solid waste generated and second is to treat pol-
luted wastewater for greener environment.
Lugo-Lugo et al. (2009) and Feng et al. (2009, 2011) use
the polymer grafted OP for the removal of heavy metals.
This enhances the adsorptive property of OP. Xanthates
are formed by hydroxyl-containing substrates present in
OP with carbon disulfide under caustic condition. These
 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent 369

Table 6: Batch adsorption studies for the removal of organic and inorganic compounds using FPW as an adsorbent.

Peel Adsorbate Modification methods Qm (mg/g) % Removal Particle size Eq. Time Co (mg/l) pH References
(mm) (min)

OP Pb2+ Natural, formaldehyde- 46.61 – – – – 5 Lugo-Lugo

treated (acetic acid) and et al. (2009)
copolymer (poly acrylamide-
cometacrylic acid)-grafted
OP Cu2+ Dried OP was treated with – 92 2 90 50 3.5 Ghosh et al.
0.05 m CaOH solution for (2013)
18 h
OP Remazol – 11.62 – 1.180–0.355 900 – – Mafra et al.
brilliant blue (2013)
BP Cr3+ Esterification was achieved 115.43±3.63 95 0.125 30 – 4 Memon et al.
by adding 9 g of washed (2008a)
and dried BP in 633 ml of
99.9% methanol, to which
5.4 ml of conc. HCl was
added then solution was
heated at 60°C and for 48 h
CP Cr 6+ – 250 – 0.15 120 200 2.0 Saha et al.
(2012)
CP MB – 344.83 – 0.5–1 315 100 6–10 Hameed
et al. (2008)
CP La3+ 154.86 > 0.355 150 20 5 Torab-
Mostaedi
(2013)
Ce3+ 162.79
PP Ni Thermally activated at 52 – 0.1–0.075 600 5.5–6.5 Bhatnagar
600±5°C for 1 h in the and Minocha
presence of air (2010)
CUP Pb2+ – 28.25 87.12 0.6–0.8 60 25 5 Pandey et al.
(2014)

Figure 3: Comparison of different FPWs for their use for the adsorption of heavy metal, dyes, organic compounds, or some other pollutants.

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370 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
xanthates have the ability to form metal complexes. So,
xanthates can eliminate the drawbacks and improve the
performances of OP for the removal of heavy metals sig-
nificantly. Sha et al. (2010) and Chen and Chen (2009)
compared the adsorptive properties of OP by its pyrolysis
treatment for 6 h at different temperatures for the removal
of organic pollutants, 1-naphthol and naphthalene. Nemr
et al. (2009) and Khaled et al. (2009a) have successfully
removed Direct Blue-86 and Direct Navy Blue 106 by
making the carbon of OP using 98% H3PO4. Biosorption of
heavy metals by pectin-rich fruit materials was found to be
most suitable. The carboxyl groups of pectin are primarily,
but not exclusively, responsible for Cd binding (Schiewer
and Patil 2008, Schiewer and Iqbal 2010). I­ zquierdo et al.
(2013) evaluated the use of OP-based adsorbents for the
removal of Cu2+ from water containing citrate and EDTA
as the main pollutants in the wastewater generated
from metal plating processes. The presence of citrate in
the wastewater reduced the uptake of Cu2+ on OP-based
adsorbents due to the presence of anionic Cu2+-chelated
species. However, EDTA strongly decreased Cu2+ uptake
for the entire concentration range considered. OP showed
good adsorption capacity for the removal of MB (Kumar
and Porkodi 2007, Foo and Hameed 2012).
Liang et al. (2013) studied the binary adsorption of
Cu2+ and Ni2+ on GP along with the individual adsorption
of Pb, Cu2+, and Ni2+. For binary adsorption, they found
that the uptake of both Cu2+ and Ni2+ ions, especially for
Ni2+, dropped quickly when Pb2+ ions existed in the solu-
tion. Also, the adsorption capacity decreases in binary
system as compared with individual adsorption. The
desorption capacity, i.e. the amount of adsorbate des-
orbed per total amount adsorbate adsorbed, of GP was
also tested. M­ assocatto et al. (2013) demonstrated that
alkaline-treated BPs are more effective than acid treated
in removing Pb2+ from aqueous solution. Jha et al. (2013)
utilized zirconium loaded OP for the removal of fluoride
ions. The efficiency is about 5.605 mg/g. Liu et al. (2013)
activated BP in microwave for 2 min at 1300 W power for
enhancing the adsorption capacity of Cr6+ and Ni2+ and
obtained the enhanced adsorption capacity of 24.13 mg/g
and 14.97 mg/g, respectively, after microwave treatment.
Ali and Saeed (2014) treated BP with alkali and acid to
enhance the adsorptive property of heavy metals.
BPs previously extracted with supercritical CO2
retained their adsorption capacity for subsequent removal
of heavy metal (Albarellia et al. 2011). Activated carbon
prepared form BP by chemical activation by H3PO4 with
relatively high surface area and pore volumes is highly
reasonable for the removal of heavy metals and oil/grease
particles from industrial wastewater (Borhan et al. 2014).
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Rafique et al. (2013) obtained the adsorption efficiency of
88% on peels of banana, lemon, and peels composite (in
the BP:LP ratio of 1:1) as possible adsorbents for the puri-
fication of industrial effluents polluted with heavy metals
like Pb, Cd, Ni, and Cu.
Zou et al. (2014) utilized PMP for the removal of
spilled oil (diesel and lubricating oil) from artificial salty
water. They found that with increasing salinity of water,
the adsorption of spilled oil increases. When the salin-
ity of water was 20–30%, oil became more hydrophobic
because of electrostatic interactions and the salting out
effect increased, increasing the sorption amount. ­Djelloul
and Hamdaoui (2014) successfully studied the batch and
dynamic adsorption of MB over MMP with a Langmuir
adsorption capacity of 333 mg/g. For removal of Pb ions
from water, cucumber peel (CUP) is another good option
(Pandey et al. 2014).
Some authors effectively used direct industrial waste-
water for experimentation purposes. The selective recov-
ery of Au3+ from the waste of printed circuit boards by
preparing BP carbon was studied by Zheng and Wang
(2013). Ramavandi et al. (2014) applied the Taguchi
method and gives a suitable approach for optimization
of percentage removal of Cr6+ by muskmelon peel/melon
peel (MMP). The applicability of MMP was tested by using
real wastewater samples obtained from a local electroplat-
ing plant for the removal of Cr6+. Cassava peel (CAP) used
in the adsorption and filtration treatment of the wastewa-
ter from the same industry revealed that the effluent from
the treatment process is suitable for irrigation (Omotosho
and Sangodoyin 2013).
Recently, various computational methods were uti-
lized for the design and optimization of adsorption process
in which FPW is used as adsorbent. Nascimento et al.
(2014a) studied the influence of the mass of the adsor-
bent, particle size, and stirring speed using a 23 factorial
design to study the adsorption efficiency of the reactive
gray BF-2R dye. Similarly, Ghosh et al. (2013) successfully
used statistical methods for optimizing the adsorption
process of Cu2+ onto modified OP. Also, artificial neural
network was implemented for designing the process mod-
eling. The response surface methodology was effectively
employed to optimize the operating parameters of Pb2+
adsorption on litchi pericarp (LPP), which might provide
a method with high accuracy and reliability for describing
the adsorption process of Pb2+ by LPP (Sun et al. 2014).
Based on the review of reported batch adsorption
studies, it is found that pollutants like Pb2+ and MB are
most extensively studied. Maximum uptake of Pb2+ was
found to be on OP as 496 mg/g and MB on jackfruit peel
(JFP) as 400 mg/g. Researchers studied the effect of pH and
 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent 371

found that pH 5–6 is optimum, while alkaline medium is
most inefficient. Equilibrium time required for FPW varies
from 7 min to 3 days; however, durian peel (DP) takes
maximum time to reach equilibrium. Most of the reported
batch studies are carried out at room temperature.
available on the use of FPW in dynamic adsorption. Some
of it has been listed in Table 7, while a more detailed
account is given in Supplemental Table S4 (supplemen-
tary information).
For increasing the capacity, Lugo-Lugo et al. (2009)
treated OP with formaldehyde and grafted with copoly-
mer. Chao et al. (2014) and Chatterjee and Schiewer (2014)

10 Column adsorption studies enhanced the adsorption capacity by treatment of solvent

extraction and alginate-immobilization of CP, respec-
tively. Marín et al. (2009), Zou et al. (2013), Sreenivas et al.
Batch adsorption studies are used for the treatment of
(2014), and Castro et al. (2011) used OP, grapefruit peel
small volumes of effluents or for laboratory purposes. It
(GFP), ash gourd peel, and BP, respectively, without any
is, however, not suitable to use at industrial scale, where
successful treatment. These untreated FPWs show good
large volumes of wastewater are continuously generated.
adsorption capacity as compared with treated peels.
So, for practical and large-scale operations, a packed
Based on the limited column studies, some conclu-
column (fixed-bed) is preferred. Packed column is gen-
sions can be drawn. Just like in batch studies, in column
erally considered as the best reactor type for wastewater
studies, also Pb2+ and MB were effectively removed.
treatment, where fresh adsorbent is always in contact with
­Fernandez et al. (2014) studied the adsorption of MB and
wastewater, providing the essential concentration gra-
rhodamine B on OP in batch as well as in column. Adsorp-
dients between adsorbate and adsorbent for adsorption.
tion capacity is reported to be 319.85 mg/g and 522.13 mg/g
This permits far more effective utilization of adsorbent
in batch and 298.751 mg/g and 199.49 mg/g in column
capacity and also results in improved effluent quality. The
for MB and rhodamine B, respectively. Column adsorp-
design and theory of packed column adsorption systems
tion capacity is measured based on breakthrough curve.
focus on determination of the shape of the breakthrough
Though the uptake capacity in column is less than in the
curve and its kinetics through the bed. The performance
batch, residence time in column is much less than that in
of fixed bed is described by the theory of the breakthrough
batch. Thus, column removes pollutants faster than batch.
curve (Zou et al. 2013, Chatterjee and Schiewer 2014,
Simate and Ndlovu 2015).
Column studies are not very popular among the
researchers using FPW. For packed-bed column applica- 11 Adsorption thermodynamics
tions, the sorbent should be sufficiently rigid. Some FPW
caused clogging and disintegration problems in packed- Temperature study helps in calculating the Gibbs free
bed reactors, though they performed well in batch mode energy (ΔG), enthalpy (ΔH), and entropy ΔS of the
(Chatterjee and Schiewer 2014). Very little literature is given adsorption process. The value and sign of these

Table 7: Column adsorption studies for the removal of organic and inorganic compounds using FPW as an adsorbent.

Peel Adsorbate Modification Qm Column Particle Flow rate Co Solution References

method (mg/g) dimensions (cm) size (mm) (ml/min) (mg/l) pH

H Di

CP Cu2+ Soxhlet extraction 98.1 3 1 0.2 2 300 5.4–5.7 Chao et al. (2014)
Cd2+ was done by adding 144
Ni2+ n-hexane and 70.2
Pb2+ ethanol in a 1:1 173
ratio (V/V) and then
dried
BP Cu2+ – – 0.28 – – 1 0.01 5.5 Castro et al. (2011)
Pb2+
BP Th – 95.34% 100 2.54 5–10 5 1 8 Abbas (2013)
removal
PUP MB – 35.98 10 1 – 1.3 50 – Djelloul and
Hamdaoui (2014)

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372 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent

parameters help in assessing thermodynamic feasibility
of the process. For a given temperature, if the ΔG value
is negative, then the process is considered to be sponta-
neous. Furthermore, the process is endothermic if ΔH is
positive and exothermic if ΔH is negative. For calculation
of ΔH and ΔS, the relationship of Gibbs free energy ΔG and
adsorption equilibrium constant Kd is found at different
temperatures. The values of ΔG, ΔH, ΔS are calculated by
using the following equations:
In contrast with this, Ajmal et al. (2000), Qin et al. (2012),
Zou et al. (2012), and Hafeez et al. (2010) found the endo-
thermic nature on adsorption. In this case, the adsorption
capacity of FPW increases with an increase in tempera-
ture. This may be due to the enlargement of pore size and/
or activation of the adsorbent surface at high temperature.

∆G0 = -RT lnK d (1)

∆S0 ∆H 0
lnK d = - (2)
R RT 
The values of enthalpy and entropy change (ΔH, ΔS)
for the adsorption processes are determined from the
slope and intercept of plot ln Kd vs. 1/T. The nature of this
plot is a straight line.
Table 8 summarizes the selected work reported in the
literature for thermodynamic studies at different tempera-
tures. Detailed thermodynamic studies are listed in Sup-
plemental Table S5 (supplementary information). Salmana
et al. (2011), Bhatnagar et al. (2010a), Memon et al. (2009),
Liang et al. (2010), and Lim et al. (2014) showed that the
adsorption capacity of an adsorbent decreases due to an
increase in temperature, indicating the exothermic nature
of the adsorption. This decrease in adsorption is either
due to the mobility of metal/dye ions in the solution,
which increases with an increase in temperature, or could
be because of the enhancement of the desorption process
as a result of the dislodgement of the adsorptive forces.
12 General mechanism involved
In biosorption, adsorption is a result of the interactions
of weak forces, chemical reactions, and ionic strength
leading to stronger binding (Achak et al. 2009). These
interactions may occur inside the pores, outside the pores,
or on the surface of FPW (Silva et al. 2013).
The mechanism responsible for the adsorption of dif-
ferent organic compounds onto lignocellulosic waste like
FPW is tough to predict. The chemical structure and the
functional groups present on the FPW surface are diffi-
cult to fix due to their different origins, types, seasonal
variations, and geographic locations. Particularly acid-
base functional groups present on the adsorbent surface
might play a vital role in ionic interactions taking place
during adsorption. These interactions help to postulate
the involved mechanism such as chemisorption, complex-
ation reactions, surface adsorption, ion exchange, diffu-
sion through pores and electrostatic interactions, or some
other. FPW contains different types of functional groups
on its surface, like carboxyl, hydroxyl, amino, thiol, etc.,
and so the binding mechanism and adsorption affecting

Table 8: Thermodynamic studies.

Peel Adsorbate ΔH ΔS ΔG (kJ/mol) References

(kJ/mol) (J/mol/K)
20°C 25°C 30°C 35°C 40°C 45°C 50°C 60°C

OP Ni2+ 53.89 0.1923 – – -4.72 – -6.55 -8.79 – Ajmal et al. (2000)

OP MB -37.39 -90.31 -10.09 -9.146 -8.04 -7.459 Kumar et al. (2014)
OP Remazol 0.24 0.97 -3.29 -4.07 -4.72 -5.36 (55°C) Bayrak and Uzgör
Black B (2013)
PMP Cu2+ -27.9 29.8 Inagaki et al.
(2013)
Cd2+ -15.7 40.2
Pb2+ -17.1 39.3
LP Co -21.2 54.61 – -37.47 – – – -38.56 – – Bhatnagar et al.
(2010a)
BP Cr6+ -30.5±5.0 0.11±0.02 – – -3.81±0.03 – – – – – Memon et al.
(2009)
PUP U6+ 14.95 130.11 130.11 – -24.47 – -25.77 – – – Qin et al. (2012)
PP Ni 8.6 144.2 – -34.4 - – – – – – Bhatnagar and
Minocha (2010)

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 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
parameters in each case also vary depending on the active
functional group (Kosasih et al. 2010, Palma et al. 2011).
Some studies on biosorption proposed that FPW can
be viewed as natural ion exchange materials, since they
contain weakly acidic, strongly acidic, and weakly basic
functional groups on its surface (Suryavanshi and Shukla
2010). The adsorption mechanism depends on the phys-
ico-chemical characteristics of FPW as well as on some
mass transport processes (Lasheen et al. 2012). This mass
transport process can be described as follows:
–– Mass transfer across the boundary layer adjacent to
the FPW particle (transport of adsorbate molecule to
the external surface of the FPW from the bulk solution
by diffusion through the liquid boundary layer)
–– Mass transfer into the particle surface (adsorbate dif-
fusion from external surface into the pores of FPW)
–– Adsorption at the active site (adsorption of the adsorb-
ate molecule on the active sites present in the pores
of FPW) (Hameed and El-Khaiary 2008, Achak et al.
2009, Foo et al. 2011).
Generally, for the adsorption of pollutants onto FPW, car-
boxylic and hydroxyl groups are found to be more respon-
sible than the other groups (sulfhydryl, thio, aldehyde,
ketones, amino, etc.) present on the surface. For metal
binding, the ion exchange mechanism is predominantly
followed. Carboxylic groups are mainly responsible for
metal binding. Pectin (Figure 4) is an anionic cell wall pol-
ysaccharide of higher plants, containing mainly galactu-
ronic acid, which has a large number of carboxyl groups.
Therefore, pectin-rich materials have a high ability for
metal binding.
A number of authors (Pavan et al. 2006, Memon
et al. 2008a,b, Iqbal et al. 2009, Liang et al. 2009b, 2010,
­Suryavanshi and Shukla 2010, Foo et al. 2011, Gustavo
et al. 2011, Kai et al. 2011, Lasheen et al. 2012, Weijun
et al. 2012, Zou et al. 2012) propose the ion exchange
mechanism for metal adsorption on FPW, whereas others
­(Ning-Chuan et al. 2010, Liang et al. 2011, Gupta and Nayak
2012, Meisam et al. 2013) argue that the metal adsorption
mechanism may be either ion exchange, or complexation,
or a combination of both. Memon et al. (2009) explains
Figure 4: Chemical structure of pectin (see Huang and Zhu 2013).
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373
complex formation mechanism for metal adsorption on
FPW. Removal of anionic pollutants is much challenging
than removal of the other pollutants. Only few papers are
available on removal of anionic pollutants using FPW.
For anionic pollutants removal, a cationic adsorbent
is needed. Therefore, sometimes, surface modification
is required for better efficiency (Silke and Ankit 2009,
Kosasih et al. 2010, Mallampati and Valiyaveettil 2013).
For dye removal, several mechanisms are proposed,
like ion exchange, chemisorption, and ionic exchange.
Hydroxyl and poly-phenolic groups on FPW are the main
binding sites for dyes. Khaled et al. (2009b) and Inbaraj
and Sulochana (2006) concluded the possibility of ion
exchange mechanism for dye adsorption, while Amin
(2009) and Khaled et al. (2009a) assume electrostatic inter-
action and chemical reaction between the dye and FPW.
Adsorption of organic pollutants is not limited to elec-
tronic interactions or chemisorption (Achak et al. 2009)
but can also be explained by donor-acceptor complex
mechanism (Bhatnagar and Minocha 2009).
Kinetic and thermodynamic modeling also gives
some idea about the mechanism involved. Particularly the
Weber-Morris intraparticle diffusion model gives an idea
about the diffusion mechanism. According to this model,
adsorption mechanism follows the intraparticle diffusion
mechanism when a plot of uptake (qt) vs. the square root
of time (t1/2) is linear; otherwise, some more steps may
be controlling (Bhatnagar and Minocha 2009). Proposed
mechanisms for FPW adsorption system for heavy metals,
dyes, and organic pollutants are summarized in Table 9.
From the study of different mechanisms reported, adsorp-
tion of organic or inorganic pollutants on FPW can be well
explained by ion exchange mechanism. Depending on the
system and given conditions, adsorption of any anion/
cation is a highly complex process as many factors are
working simultaneously to make the process viable. Along
with the physico-chemical properties of the FPW, adsorp-
tion mechanism also depends on operational parameters
as discussed in Section 6.
13 Regeneration of adsorbent
Regeneration is a process in which adsorbent loaded
FPWs are eluted by using appropriate solvent to recover
a small volume of concentrated pollutants (especially
metals). One of the important industrial applications
of adsorption is recovery of loaded pollutants from the
adsorbent and simultaneous regeneration of the adsor-
bent for reuse. The usefulness of any adsorbent depends
374 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent

Table 9: Mechanism proposed.

FPW type Adsorbate Mechanism proposed References

OP Cu2+ Ion exchange Lasheen et al. (2012)

Cd2+
Pb2+
OP Pb2+ Ion exchange, or complexation, or by a combination of both Liang et al. (2011)
processes
Zn2+
OP Mo4+ Ion exchange Weijun et al. (2012)
GFP Crystal violet Ion exchange Saeed et al. (2010)
BP Cr3+ Ion exchange Memon et al. (2008a)
BP Cr6+ Complex mechanism Memon et al. (2009)
PP 2,4-dichlorophenol Donor-acceptor complex mechanism Bhatnagar and Minocha (2009)
OP Cu2+ Electrostatic interaction and/or ion exchange, complexation, Ning-Chuan and Xue-Yi (2012)
or by a combination of all the processes
Pb2+
Zn2+
BP Cd Ion exchange Memon et al. (2008b)
GFP U6+ Ion exchange Zou et al. (2012)
GFP Cd2+ Ion exchange and complex formation Meisam et al. (2013)
Ni2+
CAP Ni2+ Chemisorption Alfin et al. (2011)
MP Cd2+ Ion exchange Iqbal et al. (2009)
Pb2+
OP Cu2+ Ion exchange Liang et al. (2010)
POP Pb2+ Electrostatic interaction Pavana et al. (2008)
PAP Cd2+ Ion exchange Foo et al. (2011)
OP Cu2+ Ion exchange and hydrogen bonding Habib et al. (2007)
PP Direct Blue 106 Electrostatic interaction and a chemical reaction between the Amin (2009)
dye and the adsorbent
OP Direct N blue 106 Electrostatic interaction and a chemical reaction between the Khaled et al. (2009b)
dye and the adsorbent
GP Fluoride anion Ion exchange Kai et al. (2011)
MMP Pb2+ Cation exchange Huang and Zhu (2013)
YPFP MB Electrostatic attraction Pavan et al. (2007)
OP Direct yellow 12 Ion exchange Khaled et al. (2009a)
JFP Rhodamine B Ion exchange Inbaraj and Sulochana (2006)
PMP Ni2+ Ion exchange Pavan et al. (2006)
Co2+
Cu2+
DP Basic green 4 Electrostatic force and chemical reaction Kamchai et al. (2010)
CP Pb2+ Ion exchange Suryavanshi and Shukla
(2010)
CFP Brilliant green Electrostatic interaction (ion exchange) Kumar and Barakat (2013)
GP Pb2+ Ion exchange Huang et al. (2013)

not only on its adsorptive capacity but also on its ability
of regeneration and reuse. This adsorbed pollutant can
be desorbed by using different physical and chemical
methods (Park et al. 2010). Generally, desorption mech-
anism is similar to that of adsorption mechanism. It
may involve complexation or ion exchange (Njikam and
Schiewer 2012). The different reagents used for desorp-
tion and regeneration of adsorbents are listed in Table 10.
Figure 5 gives the schematic flow diagram of regeneration
of FPW.
Few authors studied desorption along with adsorp-
tion. Metal ions are found to desorb more than 95%.
Researchers used FPW for 5–6 cycles and retained adsorp-
tion efficiency of more than 90%. After recovery of metal
ions, FPW can be safely burned and its heating value can
be utilized. Various chemicals like NaOH, HNO3, H2SO4,
and HCl were used in different concentrations to desorb
metal ions from FPW.
Hameed et al. (2008) opined that FPW loaded with
basic dyes need not be regenerated and can be disposed

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 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent 375

Table 10: Desorption/regeneration methods of adsorbents and

recovery of adsorbate.

Type of method Details of method

Physical Thermal (incarnation), microwave treatment,

regeneration etc.
Chemical Alkalis (NaOH, NaHCO3, etc.)
modification
Acids (H2SO4, HCL, HNO3, H3PO4, NaNO3 citric
acid, acetic acid, water-acetic acid, etc.)
Others (sodium citrate, Na2EDTA, etc.)

Used peels Drying

Physical Chemical method

treatment (Use of activating agent
(Incerination, like alkali, acids,
microwave, etc) polymers, etc)

Regenerated
adsorbent for next
Cleaning and adsorption cycle
drying
Figure 6: Overall adsorption process using FPW.

Recovered adsorbate
(metal dyes, etc.)

Figure 5: Schematic flow diagram of regeneration of FPW.
by direct burning. Detailed desorption studies are given
in Supplemental Table S6 (supplementary Information).
Approximate costing of use of activated carbon and
raw OP for removal of MB can be estimated. The adsorp-
tion capacity of activated carbon and OP is 24.8 and
18.6 mg/g (Pofgieler 1991, Annadurai et al. 2002), respec-
tively. To remove 24.8 kg of MB, the amount of activated
carbon and OP required would be 1 and 1.2 MMT, respec-
tively. The material cost of activated carbon would be
$1000, whereas costing of 1.2 MMT OP involves overhead
and grinding charges, which are much < $1000. Thus, OP
is ultra-cheaper than activated carbon; however, these
estimations are based on one-time use of adsorbents.
Reuse of activated carbon would reduce the cost differ-
ence even then OP will be cheaper than activated carbon.
In general, the overall FPW adsorption process can be
illustrated as in Figure 6.
14 Future perspectives
FPW adsorption is in its nascent stages and requires
further investigations to get insight on the process. Most
of the reported studies are focused only on batch mode.
Column studies should, however, be carried out, which
would help in scaling up and designing for commercial
applications.
FPWs are natural biomaterials. Their properties and
surface characteristics depend on various parameters like
(1) location of the source, (2) geological condition of the
location, (3) season, (4) ripening state of the fruit, and (5)
quality and type of fruit. These parameters add a compo-
nent of inconsistency in results. Work should be done on
characterization of FPW taking into account these and
other similar parameters. This data base will help in ana-
lyzing inconsistency and reproducibility of experimental
data.
Adsorption is a physico-chemical phenomenon that
depends on various parameters, and its exact mechanism
is very complex. Until now, only few studies have com-
mented and proposed probable mechanism(s). Thorough

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376 P.D. Pathak et al.: Fruit peel waste as a novel low-cost bio adsorbent
understanding of FPW adsorption mechanisms remains a
challenge.
Pretreatment of the peels increases adsorption per-
formance, but it is a costly preposition at industrial level.
Some innovative and economic processes should be
evolved for pretreatment to meet the industrial standards.
To date, FPWs are reported for their use for the removal
of heavy metals, dyes, and some organic compounds from
aqueous solutions. There is a need to explore the use of
FPW for more organic or inorganic pollutants. FPW should
also be studied for adsorption of gaseous pollutants such
as ammonia, methane, CO2, and NOX (Giraldo et al. 2014).
Apart from listed pollutants, other contaminants should
be explored for adsorption on FPW.
Detailed study on disposal of FPW after adsorption
needs to be carried out. FPW has some calorific value and
can be used in biomass gasification after adsorption.
15 Conclusion
Biosorption using FPW is a new process that has shown
good promise for the removal of different organic and
inorganic contaminants from aqueous effluents. In this
article, FPW as an adsorbent for different organic and
inorganic contaminants has been reviewed. The use of
biosorbents like FPW is suggested since they are relatively
cheap and easily available, can be easily modified, and
show good adsorption capacity for wide number of pollut-
ants. Different surface modification methods as employed
by researchers are useful for enhancement of adsorp-
tion capacity. This review article focuses on use of FPW
in batch adsorption study, which provides basic data to
design an adsorption column for industrial applications.
The following comments, not generalizations, can be
made from the large number of articles reviewed:
–– Heavy metals, dyes, and organic pollutants can be
successfully removed from aqueous solution using
FPW. Heavy metals show higher affinity toward FPW.
–– Wide varieties of FPW are used for the adsorption
study. OP and BP are most efficient for removal of Pb2+
and MB.
–– Cationic pollutants are more efficiently adsorbed on
FPW.
–– Treated/modified FPW shows better adsorption
capacity as compared to raw or untreated ones. Pol-
yacrylic acid grafted and cellulose extracted FPWs
are more efficient in removal of heavy metal pollut-
ants. For dye removal, acid treatment was found to
be effective. However, this area demands more work.
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With surface modification, uptake capacity is found
to increase by an order of magnitude.
–– Pseudo-second-order kinetic model fits better than
other kinetic models. From the Weber-Morris intra-
particle diffusion model curve, it is confirmed that dif-
fusion is not the only rate controlling step and more
than one factor affects adsorption on FPW.
–– The Langmuir and Freundlich models were applied
in most of the systems. Out of these two models,
­Langmuir fits better than Freundlich, which suggests
that adsorption on FPW is monolayered.
–– FPW batch adsorption process is carried out most
­efficiently between the pH range of 5 and 6, at room
temperature, with agitation speed 200–300 RPM.
–– A thermodynamic study tells us about the exother-
mic or endothermic nature of adsorption. Generally,
adsorption is exothermic in nature. However, some
adsorption studies show endothermic nature, which
is contradictory to usual nature.
–– Metal ions are found to desorb more than 95%.
Researchers used FPW for five to six cycles and retain
adsorption efficiency more than 90%. After recov-
ery of metal ions, FPW can be safely burned, and its
heating value can be utilized. Various chemicals like
NaOH, HNO3, H2SO4, and HCl were used in different
concentrations to desorb metal ions from FPW.
–– Although the reproducibility of the results is poor,
FPW has a great potential in wastewater treatment
due to its abundant and cheap availability. FPW can
be used for removal of heavy metals and dyes; how-
ever, removal of organic and gaseous impurities
needs further investigation.
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Bionotes
Pranav D. Pathak
Visvesvaraya National Institute of
Technology, Department of Chemical
Engineering, South Ambazari Road, Nagpur,
Maharashtra 440010, India
Pranav D. Pathak is presently working as a Research Scholar at
Visvesvaraya National Institute of Technology, India. His research
interests include adsorptive separation and use of biomass for
wastewater treatment. He received his undergraduate and post-
graduate degrees from Sant Gadge Baba Amravati University, India.
He has attended several national and international conferences.
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381
Sachin A. Mandavgane
Visvesvaraya National Institute of
Technology, Department of Chemical
Engineering, South Ambazari Road, Nagpur,
Maharashtra 440010, India,
sam@che.vnit.ac.in
Sachin A. Mandavgane is an Associate Professor in the C ­ hemical
Engineering Department at Visvesvaraya National Institute of
Technology, India. He received his undergraduate, postgraduate,
and doctoral degrees from Laxminarayan Institute of Technology,
India. His research interests include adsorptive separation, solid
waste utilization, use of biomass for different applications, Indian
traditional knowledge, and engineering education. His teaching
interests include use of social media for teaching, undergraduate
research, and bridge building between school and engineering
students.
Bhaskar D. Kulkarni
CSIR-National Chemical Laboratory,
Pune 411008, India
Bhaskar D. Kulkarni is presently working as a CSIR-distinguished
Scientist, Engineering Sciences, at CSIR-National Chemical
­Laboratory, Pune, India. His research interests include math mod-
eling and simulations of chemical reactions and reactors including
biological systems and processing and use of biomass for different
applications. He has published over 325 publications in interna-
tional journals and has several patents to his credit. Dr Kulkarni
has guided over 65 students for their doctoral thesis. He is a fellow
of national academics in India and also a fellow of the Third-World
Academy of Sciences.