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Applications of egg shell and egg shell membrane as adsorbents: A review

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DOI: 10.1016/j.molliq.2016.08.065

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 Journal of Molecular Liquids 223 (2016) 376–387

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Journal of Molecular Liquids

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

Review

Applications of egg shell and egg shell membrane as adsorbents:

A review
Alok Mittal a,⁎, Meenu Teotia b, R.K. Soni b, Jyoti Mittal a
a
Department of Chemistry, Maulana Azad National Institute of Technology, Bhopal 462 003, India
b
Department of Chemistry, Ch. Charan Singh University, Meerut 250 004, India

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

Article history: Worldwide consumption of hen eggs is quite high, which results into availability of large amount of discarded egg
Received 25 May 2016 wastes, particularly egg shell (ES) and egg shell membrane (ESM). Disposal of ES and ESM is always a problem
Accepted 18 August 2016 particularly to the authorities of food, bakery and poultry units. In recent years, attempts have been made to uti-
Available online 20 August 2016
lize ES and ESM for the production of biodiesel and collagen but results are not much economically viable.
In the hunt of waste materials as potential scavenger of hazardous chemicals, ES and ESM have emerged as non-
Keywords:
Egg shell
toxic, versatile and efficient adsorbents. Last 10 years have witnessed a systematic growth in the use of ES and
Egg shell membrane ESM as adsorbents for the removal of variety of organic as well as inorganic hazardous chemicals, particularly
Bio-waste material from wastewater. Literature survey reveals that ES and ESM in their natural as well as chemically modified
Adsorption forms have provided excellent results for the removal of various classes of dyes, oxalic acid, phenol, pesticides,
Adsorbent humic acid, pharmaceutics, surfactants, PAHs, heavy-, precious- and light- metals, actinides, fluorides, etc. In re-
cent years powdered ESM have been modified to nano-particles and used as adsorbent in various interesting ap-
plications. Reports are also available on the use of nanostructured material CHAP, derived from ES, for the
removal of cadmium and lead ions from waste water.
Present review article is an attempt to summarize the research carried out on the above mentioned applications
of ES and ESM. Overall 108 research articles have been included in this review, which describe a methodical
growth in the subject matter.
© 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2. Anatomy of egg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2.1. Egg shell (ES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2.2. Eggshell membrane (ESM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
2.3. Chemical composition of ES & ESM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
3. Review of literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
3.1. Adsorptive removal of organic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
3.1.1. Natural ES and ESM as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
3.1.2. Chemically modified ES & ESM as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.2. Adsorptive removal of inorganic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
3.2.1. Natural ES & ESM as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
3.2.2. Chemically modified ES & ESM as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
3.3. Applications of ESM nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
3.4. Carbonate hydroxylapatite as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

⁎ Corresponding author.
E-mail addresses: aljymittal@gmail.com (A. Mittal), teotiameenu@gmail.com (M. Teotia), rksoni_rks@yahoo.com (R.K. Soni), jyalmittal@yahoo.co.in (J. Mittal).

http://dx.doi.org/10.1016/j.molliq.2016.08.065
0167-7322/© 2016 Elsevier B.V. All rights reserved.
 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
1. Introduction
Removal of toxic pollutants from the industrial, municipal and other
waste solutions is the cause of global concern. Presence of toxic
chemicals in the environment poses significant environmental hazards,
as these chemicals ultimately reach and accumulate in animal and
human tissues. In order to minimize this threat several physico-chemi-
cal methods, such as reverse osmosis and ultrafiltration, oxidation/re-
duction, precipitation, adsorption electrodialysis etc. have been
employed [1–4]. Among all these methods, adsorption has gained tre-
mendous importance due to its high efficacy, cost-effectiveness, versa-
tility and easy handling [5]. Unlike many other degradation methods,
adsorption does not leave behind any toxic intermediate(s) or
byproduct(s) of particularly complex organic pollutants. Moreover, as
globally environmental standards are getting more and more stringent,
technical applicability and financially viability have become the key fac-
tors, while selecting a suitable treatment process. Conventional
physico-chemical treatment methods also involve careful disposal, in-
complete removal, requirement of high energy and costly chemicals
and reagents, which escalates the treatment cost, reduces the efficiency
of the process and produce other toxic waste products [1,2]. Therefore
adsorption is the final choice, which has been universally accepted by
the world environmentalists for the disposal of hazardous and toxic in-
organic as well as organic pollutants present in various effluents.
One of the key factors associated with the adsorption process is the
selection of adsorbent, which ultimately decides the economics, effi-
ciency and versatility of the process. The first documented adsorption
has been carried out by employing charcoal as adsorbent [6]. Over sev-
eral decades, with availability of very limited choices of adsorbents, ‘ac-
tivated carbon’ despite an expensive material has been widely used as
adsorbent for the removal of various pollutants. Of course high cost of
activated charcoal restricted its applications and therefore over the
years the focus of research has been shifted to replace commercially
available activated charcoal by suitable low cost alternatives, preferably
waste materials [1,2]. As far as substitute adsorbents are concerned, as-
sociated history has been summarized in several books, reviews and
monographs [7–14]. In nut shell it can be narrated that at least past
two decades have witnessed emergence of large number of low cost ad-
sorbents and biosorbents derived from industrial, agricultural and other
natural waste materials as potential adsorbents for scavenging different
varieties of toxic pollutants [7–14].
With the advent of use of waste materials as adsorbents several us-
able bio-wastes obtained from humans, birds and animals like hairs,
feather, nails, horns etc. have been used as potential adsorbents for
the removal of inorganic and organic compounds [15–18]. Egg shell
(ES) and egg shell membranes (ESMs) are waste materials emerging
out in large quantities from sources such as poultries, homes, restau-
rants, bakeries and food manufacturing units [19]. Out of these sources,
bakeries and food industry gives largest chunk of ES and ESM and their
disposal is always been a challenge to the concerned authorities [20].
The cost associated with egg waste disposal is expected to increase
with increase in landfill taxes. Many investigations have been conduct-
ed to explore usefulness of egg waste such as to increase the mineral
content of compost, to deter slugs and snails, as fertilizer, as a feed for
aviary bird, cement additive to increase its strength, biodiesel [21] and
to produce collagen from ESM [22] etc. However, a study conducted in
2002 [23] claims that the disposal methods for waste ES are 26.6% as fer-
tilizer, 21.1% as animal feed ingredients, 26.3% discarded in municipal
dumps, and 15.8% used in other ways. In the last decade utilization of
poultry waste in waste water treatment has attracted much attention
from research teams all over the world.
This review article aims to give comprehensive account of utilization
of ES and ESM, derived from poultry waste, in removal of hazardous in-
organic as well as organic pollutants, particularly from their aqueous so-
lutions. The review article is divided into four major sections. The first
section describes introduction on the subject matter, while fourth
377
section incorporates the conclusions drawn on the research carried
out so far in this area and future challenges. The second section mainly
presents anatomy of egg, which includes detailed description of egg, ES
and ESM and their chemical compositions. The third section includes
the highlights of the work carried out by taking ES and ESM as adsor-
bents. For the benefit of readers this section is further divided into
three sub sections, which present literature review of removal of organ-
ic and inorganic pollutants using ES and ESM and some other novel ap-
plications of ES and ESM, respectively. In all the three sub-sections, the
highlights of available literature review are placed quite systematically
in different categories and types of pollutants. For example, use of ES
and ESM for the removal of organic compounds like dyes (acidic/
basic/azo and styryl pyridinium dyes), pharmaceutics (morphine), phe-
nol, pesticide (malathion) and humic acid is presented first followed by
the role of chemically modified ES and ESM for the removal of organic
compounds like anionic dyes, surfactants (linear alkyl benzene
sulphonates) and polycyclic aromatic hydrocarbons (PAHs). Similarly
in the second subsection description on the application of ES and ESM
as adsorbents for the removal of inorganic pollutants like Cr, Cu, Cd,
Pb and precious metals, actinides and fluorides is presented prior to por-
trayal of research on the adsorption over chemically modified ES and
ESM for the removal of toxic inorganic pollutants like Cr, Cu, Pb, As,
Hg and Au. The third subsection is devoted to some recent interesting
researches, where ESM nanoparticles have been utilized for various
other interesting (though limited) applications like fabrication of fuel
cell, bio-templates and water purifier. Overall 108 research articles
have been included in this literature review. The review article is a
thoughtful attempt of authors to present up-to-date information on
the subject matter. The article meticulously describes future prospects
and challenges associated with egg waste materials and presents sys-
tematic growth of research in this area.
2. Anatomy of egg
Birds, reptiles and fishes are those living species which produce a
hard shelled egg to develop outside female body. Every egg is self
contained and does not require any external nutrient. ‘Oology’, the sci-
ence of anatomy and physiology of eggs, descries that every egg consists
of mainly four basic structures, a protective layer (ES), a membrane as-
sociated with shell, an egg white (albumen) and yolk (vitellus). Fig. 1
gives an illustrative view of the framework of the egg. The usefulness
of the egg is mainly due to protein and nutrients present in liquid
state as egg white and egg yolk, while the solid protective layer (ES)
and its associated membrane (ESM) are usually thrown in the waste
basket.
2.1. Egg shell (ES)
The hard protective cover of the egg, the ES, consists of three layers,
the outermost layer, ‘Cuticle’, beneath to cuticle is the calcium carbonate
layer, ‘Testa’, and finally the innermost layer, ‘Mammillary layer’. Cuticle
Eggshell
Fig. 1. Egg and eggshell structure.
378 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
is dried mucus, which is laid down by the bird's uterus. It serves to pro-
tect embryo from bacterial infections and regulate evaporation of mois-
ture. Testa provides calcium to the growing egg and helps in coloration
of egg. However, Mammillary layer gives foundation to the testa and
makes direct contact with the shell membranes.
Both Cuticle and Mammillary layers together form a matrix com-
posed of protein fibers, which is bonded to calcite (calcium carbonate)
crystal. The two layers are also constructed in such a manner that
there are numerous circular openings (pores), which allow transpira-
tion of water and gaseous exchanges, throughout the shell. Each ES
has been estimated to contain between 7000 and 17,000 pores [24].
The outer surface of the ES is covered with a mucin protein, which
acts as a soluble plug for the pores in the shell.
Different birds have different thicknesses of the shell of their egg. Os-
trich, chickens, ducks, etc. have very thick ES, while small birds like
hummingbirds, sparrows, finches, etc. generally have very thin ES. It is
speculated that thickness of the ES is due to absorption of more calcium
from the shell during the growth of an egg. The size of the egg depends
upon the size of the yolk, while shape of an egg resembles a ‘Prolate
Spheroid’ with one end larger than the other and cylindrical symmetry
along the long axis. There are few species like owls, which lay very
round eggs on the other hand fast-flying, stream-lined birds like swifts
and swallows lay long and elliptical eggs. Interestingly, the color of the
ES varies with species and breeds from white, to every color of the rain-
bow. The coloration of the egg is caused due to deposition of pigment
during formation of egg in oviduct. Apart from common white some at-
tractive egg colors are shiny, emerald green, blue, greenish-black,
creamy beige, brownish-orange, brown with black markings and eggs
with red tint. It is presumed that egg color and markings help the bird
to camouflage and protect the eggs from their enemies.
2.2. Eggshell membrane (ESM)
There are two membranes which lie directly beneath the shell and
these are conveniently called inner and outer shell membranes. The
outer shell membrane remains adhered to the mammillary layer of
the shell, while inner shell membrane surrounds the liquid of the egg.
It is also pertinent to note that these two membranes separate at the
larger end of the egg and create a space between them called as ‘Air
Cell’. This air cell is formed due to contraction and cooling of egg con-
tents after it is laid by the bird. The ESM is a clear thin film lining the
ES and visible on peeling the boiled egg.
ESM possesses porous and fibril structure, which is responsible for
its good adsorption properties. It is an amorphous natural biomaterial
with an intricate lattice of stable and water insoluble fibers [25]. It is
usually light pink double layered membrane and each of these mem-
branes is composed of protein fiber that is arranged so as to form a
semi-permeable membrane. The total thickness of these two mem-
branes is about 100 μm.
2.3. Chemical composition of ES & ESM
Major constituents of the ES are carbonates, sulphates and phos-
phates of calcium and magnesium and organic matter. Traces of Na, K,
Mn, Fe, Cu, and Sr metals are also present in ES [26]. The density of ES
is about 2.53 g/cm3, which is significantly larger than that of ESM
(1.358 g/cm3). Major Constituents of ES are calcium carbonate (94%),
organic matter (4%) calcium phosphate 1% and magnesium carbonate
(1%). ESM possesses nearly 60% protein {collagen (35%), Glucosamine
(10%), chondroitin (9%) and hyaluronic acid (5%)} along with other in-
organic components like Ca, Mg, Si, Zn, etc. in smaller quantities [27–
29].
The membrane surface bears positively charged sites produced by
basic side chains of amino acids. It has a very high surface area with spe-
cial functional groups such as hydroxyl (−OH), thiol (−SH), carboxyl
(− COOH), amino (− NH2), amide (− CONH2) etc., which strongly
interact with some chemical species present in the albumen. Due to
the presence of various functional groups, ESM acts as a potential
adsorbent.
3. Review of literature
Surface analysis of ES and ESM indicates that these are porous mate-
rials and therefore can also be utilized as effective adsorbents. Thus use
of ES and ESM as adsorbents serves two purposes, as cost effective and
necessitous removal of hazardous chemicals and lessening of the
landfill's loads. Adsorption is a well established eco-friendly and clean
technology, whereas egg waste materials have been utilized as effective
alternatives to the existing adsorbents. Thus over the last one decade
egg waste materials, particularly ES and ESM have been used in waste-
water treatment to remove organic and inorganic hazardous sub-
stances. In recent years, chemically modified adsorbents have
attracted considerable attention. Several attempts have been made to
chemically modify ES and ESM to achieve either selective or/and im-
proved adsorption. With the invention of nanoparticles as superior
technology, ESM nanoparticles have also emerged as useful adsorbent
material and few interesting researches have been witnessed very re-
cently. All these available reports on the use of ES and ESM as adsor-
bents are summarized in the following paragraphs.
3.1. Adsorptive removal of organic pollutants
Industrial effluents contain variety of organic pollutants such as
dyes, pesticides, aromatic compounds (phenol), detergents, humic
acid etc. and this is mainly due to extensive use of organic chemicals
in many industries such as food processing, cosmetics, paper, textile,
fertilizer etc. A large number of these organic substances are highly
toxic and pose serious health hazard to aquatic living organisms, ani-
mals and humans. The fact that many of such organic substances are
carcinogenic and mutagenic in nature and severely effect human life
cannot be neglected. Keeping these in view it is highly essential to erad-
icate these organic substances from waste water before it is discharged
to water courses [30] and adsorption has been found most effective and
versatile in this task. In the hunt of economic adsorbent, egg waste ma-
terials, particularly ES and ESM have been found excellent scavengers
for the organic compounds such as dyes, surfactants, phenols, humic
acid and pesticides.
3.1.1. Natural ES and ESM as adsorbents
3.1.1.1. Organic dyes. Acidic dyes are one of the most important dyes
which are widely used in the textile dyeing industries. They possess
high solubility in water and strong affinity towards amphoteric fibers
like wool, acrylic, silk etc. Due to their high solubility in water their re-
moval by common physico-chemical methods is difficult, while adsorp-
tion over ES, ESM and ES–ESM mixture has proved its ability to remove
toxic acidic dyes effectively and efficiently. The adsorption characteris-
tics of C.I. Reactive Yellow 205, an acidic dye, showed that ES and ESM
are useful materials for the removal of Reactive Yellow 205 dye from in-
dustrial waste water [31]. Adsorption affinity of the dye is found to de-
pend upon the nature of charge of the adsorbent, hence on the pH of the
solution. Within initial range of concentration (20–100 mg/L) over 72 to
99% of the dye was adsorbed at equilibrium. The adsorption capacities of
ES, ESM and ES–ESM mixture were found to be 32, 34, and 185 mg/g, re-
spectively, proving thereby greater adsorption affinity of ES and ESM
mixture for the Reactive Yellow 205 dye than ES or ESM separately. In
two reports published in the years 2006 and 2008 Arami and coworkers
[32,33] established ESM as natural and eco-friendly adsorbent material
for the removal of few acidic dyes. In the first report [32] adsorption ca-
pabilities of ESM to remove dyes Direct Red 80 and Acid Blue 25 from
their aqueous solutions were established through Langmuir, Freundlich,
BET, Redlich-Peterson and Tempkin adsorption isotherm equations and
 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
it was found that adsorption of both the dyes onto ESM perfectly obeys
Redlich-Peterson adsorption isotherm. The pH studies reveal that the
adsorption capacities of both the anionic dyes onto ESM increased
with decreasing pH of the solution, while for desorption reverse trend
was observed. It was found that in the basic medium at pH 12, maxi-
mum desorption (≥81.8%) was achieved for both dyes, it is due to signif-
icantly high electrostatic repulsion between the negatively charged
surface of the adsorbent and anionic dyes, which resulted into high de-
sorption rate of dyes. In another study Arami et al. [33] carried out ad-
sorption of dyes Acid Red 14 and Acid Blue 92 (AB92) onto the
microporous and mesoporous ESM in aqueous solutions in the batch
systems. Detailed research studies include effect of initial dye concen-
tration, pH, contact time, particle size and biosorbent dosage on the ad-
sorption of the undertaken dyes over ESM at 20 ± 1 °C temperature.
Paper also includes characterization of ESM by using Fourier transform
infrared (FT-IR) and scanning electron microscopy (SEM). The surface
area of ESM was also evaluated and found to be 2.2098 m2/g. The pseu-
do-first-order, pseudo-second-order kinetics and the intra-particle dif-
fusion models were used to describe the kinetics data. Like previous
report [33], equilibrium adsorption isotherms were analyzed for Lang-
muir, Freundlich and Redlich–Peterson adsorption models and the ex-
perimental data were found well fit on Redlich–Peterson adsorption
isotherm model. As far as desorption is concerned at pH 12 maximum
desorption, around 89.6% was achieved for Acid Red 14 and 82.8% for
Acid Blue 92 in their aqueous solutions. In another work, Tsai et al.
[34] studied detailed adsorption characteristics of Acid Orange 51 onto
ES particles and compared the data with the adsorption of basic dye
Methylene Blue. It was found that at neutral pH, the dye Acid Orange
51 possess better adsorption ability over ES (about 60%) than Methy-
lene Blue (about 10%). The feasibility of ES for the removal of another
acidic dye, Reactive Red 123 from its aqueous solutions has also been in-
vestigated by Ehrampoush et al. [35]. Experimental data were analyzed
with Langmuir, Freundlich and Temkin adsorption isotherm models and
found in good concordance with Langmuir and Freundlich models
(R2 N 0.90). Interestingly, increase in ES dosage and the solution temper-
ature beyond 45 °C decreases the adsorbed dye per gram of adsorbent,
however, increase of pH of solution up to 9 results into improvement
of the dye adsorption over ES. The kinetic studies revealed that the ad-
sorption of Reactive Red 123 was rapid and obeyed pseudo-second
order rate kinetics with the kinetic constant of 0.02 g/mg·min.
Basic dyes are popular due to their low cost, wide shade range,
brightness of colors, moderate substantivity and high tinctorial
strength. Methylene Blue is one of the most important basic dyes,
which is widely used in textile dyeing industries as well as in analytical
laboratories. It is a well known fungicide, which is used for the protec-
tion of aquatic animals particularly fishes. One of the early attempts to
remove Methylene Blue by adsorbing over ES and ESM was conducted
by Tsai et al. [36]. The experiments demonstrate that ES and ESM exhibit
excellent adsorption abilities at 25 °C and can uptake 1.0 mg/g of Meth-
ylene Blue dye from its aqueous solutions. The research group also char-
acterized ES and ESM chemically and physically and paper includes
results on these studies. Salman et al. [37] examined the use of ES and
ESM and their mixture to scavenge three different dyes, Methylene
Blue (cation), Bromophenol Blue (anion) and Methyl Orange (anion)
from their aqueous solutions. It was found that ESM possesses greater
affinity towards Methylene Blue than other two dyes. It was also
ascertained that as compared to ES and the mixture of ES and ESM,
ESM alone possesses higher capacity (about 1.35 to 1.65 fold) to adsorb
Methylene Blue. The optimum conditions for highest percentage re-
moval of Methylene Blue were observed with particle size of 250 μm,
pH 10, at 80 °C, for 30 min with 1.0 g/100 ml adsorbent and 2 mg/
100 ml dye concentration. This approach was further improved by
Nagadi et al. [38] by varying the operating parameters like contact
time, pH, dosage of ES powder and temperature. Results obtained indi-
cated that the best operating conditions for the removal of Methylene
Blue are at pH 10 and temperature 50 °C by using 2 g of ES powder for
379
30 min equilibrium time. Pseudo second order kinetic model was
found to describe the ongoing adsorption process.
Literature survey reveals that very limited work has been done so far
to remove azo dyes using egg waste materials as adsorbents. Liu ana-
lyzed the adsorption and decolorization of water-soluble azo dye
Eriochrome Black T [39] and Eosin [40] on ESM and achieved about
95% of removal of Eriochrome Black T from its acidic solution and almost
same amount of removal for Eosin from its monohydrate solution.
Styryl pyridinium dyes have a large number of industrial applica-
tions like in photoresists, electrophoresis, in the production of
photoconducting layers, dying of paper etc. [41]. It is interesting to
note that ES particles potentially adsorb even the traces of styryl
pyridinium dyes from their aqueous solutions. As reported by Guru
and Dash [42], nearly 20% of the typical cyanine dye styryl pyridinium
was removed from its aqueous solution at 25 °C, 200 mg of ES particle
in fixed dye concentration of 2 × 10−5 M. Authors further studied the
effect of kosmotrophs and chaotrophs on the adsorption process of
styryl pyridinium dye by ES particles. Hydrogen bonded structure of
aqueous medium was found to affect the extent of adsorption signifi-
cantly. The extent of adsorption of styryl pyridinium dye capable of hy-
drogen bonding with water molecules in solution increases with
addition of kosmotroph (water structure making salt) such as sodium
chloride and decreases on addition of chaotroph such as potassium
chloride and ammonium thiocyanate (water structure breaking salt).
Kosmotrophs enables water molecules bound with each other through
extensive hydrogen bonding, which changes the solvation pattern of
the dye molecules leaving them free to adsorb on the surface of ES par-
ticles. If the dye is unable to form hydrogen bonds with water molecules
then the addition of kosmotroph or chaotroph is not so effective in
changing the solvation pattern of the dye. However a marked increase
in adsorption capacity for the dye is due to partial neutralization of
the surface of adsorbent leading to reduction in repulsive forces
among adsorbate and adsorbent.
The anthraquinone dyes are also called vat dyes and well known for
their brilliant colors. Though these dyes possess poor solubility in water
but can dissolve after the treatment with a reducing agent, usually sodi-
um hydrosulfite. Attempts have also been made to remove anthraqui-
none class of dyes, alizarin (1,2-dihydroxyanthraquinone) and 2-
aminoanthraquinone using ES as an adsorbent [43]. Preliminary studies
were made and optimum conditions for the dyes removal were
established through pH, concentration, temperature, contact time and
ES dosage studies and maximum adsorption was observed at pH 7 in
30 min. The amount of dye uptake was also found to increase with in-
creasing dye concentration and decrease with increasing amount of ad-
sorbent. The data were found fit in the Langmuir and Freundlich
adsorption isotherm models and it was concluded that powdered ES is
a good choice for the removal of alizarin.
3.1.1.2. Oxalic acid. Oxalic acid is a useful laboratory chemical, which is
largely used as cleaning or bleaching agent, especially for the removal
of rust by easily complexing with iron. It is also used as mordant in dye-
ing processes and plays an important role in the metallurgy of lantha-
nides. A high concentration of Oxalic acid can be harmful to humans
and animals. It is extremely destructive to the tissues of mucous mem-
branes and upper respiratory tract. On ingestion, it causes congenital
malformation to the fetus.
Powdered chicken ES of 125 μm sieve size were used to adsorb oxalic
acid from waste water and kinetics of the process was monitored under
batch technique at different temperatures [44]. The adsorbent was char-
acterized through BET surface area, SEM, FTIR and EDS techniques. Pre-
liminary investigations of the ES – Oxalic acid adsorption was
determined with respect to acid concentration and equilibrium time.
Freundlich, Langmuir, Tempkin and Harkins-Jura adsorption isotherm
models were applied to investigate the ongoing adsorption process.
Paper also contains results on the intra-particle diffusion, Elovich and
Bhangam models and calculation of various thermodynamic parameters
380 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
(ΔH≠, ΔS≠ and ΔE≠). It was concluded that that the Oxalic acid – ES ad-
sorption process was feasible and spontaneous.
3.1.1.3. Phenol. Phenol is also one of the toxic organic pollutants present
in the effluents of textile, petrochemicals, pesticides, etc. industries and
causes serious environment threats to the human beings [45–47]. Its
halogen derivatives give a peculiar smell and taste in the water and
also pose severe environmental havoc. Because of the toxic nature of
phenol, it has been designated as a priority pollutant worldwide [48].
In the year 2012, Daraei et al. [49] explored the potential of ES waste
in the removal of phenol from its aqueous solutions. Batch experiments
were conducted to evaluate the effect of pH, phenol concentration, dos-
age of adsorbent, and contact time on the removal of phenol. In-depth
kinetic studies of the adsorption process were carried out and ES was
also characterized using scanning electron microscopy, Fourier trans-
form infrared spectroscopy, X-ray diffraction, and X-ray fluorescence
analysis etc. Nearly 0.55 mg/g adsorption capacity was observed at con-
tact time 90 min, 25 °C, pH 9, adsorbent dosage 3.5 g and initial concen-
tration of phenol 30 mg/L. The adsorption of phenol over ES was found
to be an exothermic and spontaneous process. Boukhlifi et al. [50] fur-
ther performed experimental investigations on adsorption and kinetic
studies of phenol adsorption and found ES as a potent, natural and
eco-friendly adsorbent material for the adsorption of residual phenol
from effluents.
3.1.1.4. Pesticide (malathion). Elwakeel and Yousif [51] investigated ad-
sorption behavior of Malathion, a commonly used pesticide, on ES and
its thermally treated samples, using batch method and also analyzed
the adsorption kinetics as well as adsorption isotherms. The uptake ca-
pacity of ES was found up to 1.928 mmol/g at 25 °C. The adsorption pro-
cess followed pseudo first order kinetics and the uptake capacity of egg
shell was found higher after thermal treatment.
3.1.1.5. Humic acid. Humic acid is also one of the main components of
peat water having a backbone of aromatic and aliphatic residues with
numerous substituents such as –OH groups, ketones, carboxylic acid
groups, amino acids/peptides, saccharides, and amino saccharides. It
consists of large molecules with molecular weights ranging from thou-
sands to hundreds of thousands and imparts brown or yellow color in
peat water. It poses serious environmental problem in drinking water
because of its bad taste and odor [52].
Zulfikar et al. [53] proposed a new approach to remove humic acid
from peat water using ES powder. Kinetics of adsorption, influences of
pH, contact time, dosage of ES and temperature were studied and
established ES as a highly potential adsorbent for the removal of
humic acid. 5 g of the powdered ES adsorbed nearly 95% of humic acid
successfully from the peat water. From Langmuir model, the adsorption
capacity of ES for humic acid uptake was found to be about 126.58 mg/g
at pH 4.01. The kinetic experimental data proportionally correlated with
the pseudo second order kinetic model with a rate constant in the range
of 0.016–0.112 g·mg−1 min−1, while intra-particle diffusion was the
main rate determining step in the humic acid removal process.
3.1.2. Chemically modified ES & ESM as adsorbents
3.1.2.1. Organic dyes. Elkady et al. [54] immobilized ES with a polymer
mixture of alginate and polyvinyl alcohol and developed a biocomposite
adsorbent (ES composite) for the adsorption of C.I. Remazol Reactive
Red 198 from its aqueous solution. The ES composite thus formed was
characterized using XRD, TGA, FTIR and SEM. The Reactive Red 198
dye adsorption onto the ES composite was investigated in a batch sys-
tem with respect to initial dye concentration, pH, contact time, agitation
speed, temperature and adsorbent dosage. The prepared biocomposite
was found to exhibit high efficiency for the dye adsorption and the equi-
librium state could be achieved in 3 h. The maximum monolayer dye ad-
sorption capacity was estimated to be 46.9 mg/g at 22 °C and pH 1.0. The
kinetic study revealed that pseudo second order model fitted well in ki-
netic data, while both the intra particle diffusion and Boyd's kinetic
model indicated that intra particle diffusion was the rate determining
step in the ongoing biosorption process. The negative values of both
the enthalpy (ΔH°) and Gibbs free energy (ΔG°) changes indicate exo-
thermic as well as feasible and spontaneous nature of the biosorption
process.
3.1.2.2. Removal of pharmaceutics (morphine). Extracted from poppy
straw of the opium poppy, Morphine is a well-known pain reliever.
On administration, it attacks the central nervous system (CNS) and de-
creases the feeling of acute pain as well as chronic pain. Morphine is also
frequently used for relieving pain from myocardial infarction and dur-
ing labour.
In a recent study, ESM has been used for the extraction of morphine
in biological samples in a solid phase extraction (SPE) format followed
by HPLC [55]. The extraction and determination of morphine is very im-
portant for the assessment of analgesics. The chemically modified ESMs
have been developed by increasing the hydrophobicity through the re-
action of surface amino groups and glutaraldehyde followed by subse-
quent functionalization using different amines. The removal
performance of ESM was increased from 72 to 88.93% after chemical
modification. The normal hexane amine functionalized ESM with glu-
taraldehyde has shown best results in terms of analytical performance
as observed from HPLC chromatograms. These modified amine ESMs
are excellent SPE format adsorbents for extraction of morphine from sa-
liva samples.
3.1.2.3. Linear alkyl benzene sulphonates. The intricate lattice network
structure of ESM exhibits unique ability to capture linear alkylbenzene
sulfonates (LAS) by hydrophobic interactions, at pH very close to the
isoelectric point of ESM. This phenomenon is similar to the most widely
used trapping mechanism of SPE used for the extraction of LAS. Hence,
ESM has also been evaluated as bioadsorbent in SPE format for the ex-
traction of LAS [56]. Captivatingly, ESM based adsorbents are found to
possess low limits of detection, wide linear range, good precision and
recoveries under the optimal solid phase extraction conditions. ESM ex-
hibits higher extraction recoveries for LAS in the environmental sam-
ples. It also shows stronger retention abilities than conventional SPE
adsorbents, usually alkyl bonded silica and some nanostructured mate-
rials, hence can be used to enhance the recovery of LAS. On the basis of
HPLC separation and UV detection of LAS homologues, the proposed
system could respond down to 0.027 ng mL−1 of LAS with a linear cal-
ibration range from 0.2 to 100 ng mL−1, showing thereby a good LAS en-
richment ability of ES membrane biomaterial with high sensitivity, and
could be successfully used for the detection of residual LAS in environ-
mental water samples. ESM is found highly sensitive for the detection
of LAS and the adsorption capacity was found in the range 30–50 μg/g,
which is much higher than traditional SPE adsorbents. Furthermore
ESM is economical and easily available and can be modified according
to the need of the experiments.
3.1.2.4. Polycyclic aromatic hydrocarbons (PAHs). PAHs are produced
from the incomplete combustion of organic matter. Despite non polar
and lipophilic nature and poor solubility in water, PAHs persist in the
environment. They are carcinogenic and also linked to development of
cardiovascular diseases in humans.
In a recent study, based on ESM templating of LAS, Wang et al. [57]
demonstrated SPE format for the enrichment of PAHs in environmental
aqueous samples. The effect of various factors, including solution pH,
LAS concentration, ionic strength, and humic acid concentration on
the recoveries of PAHs were investigated and optimized. Authors con-
cluded that LAS concentration and solution pH had prominent effect
on extraction of PAHs, while the recoveries of PAHs decreased in the
presence of salt and humic acid. Under the optimized analytical condi-
tions, the present method could respond down to 0.1–8.6 ng/L PAHs,
 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
with a linear calibration ranging from 0.02 to 10 μg/L; showing thereby a
good PAHs enrichment ability with high sensitivity. The developed
method was used satisfactorily for the detection of PAHs in environ-
mental water samples.
3.2. Adsorptive removal of inorganic pollutants
In the last almost 10 years, utilization of poultry waste in waste
water treatment for removal of toxic metals has attracted much atten-
tion from the researchers all over the world. This section aims to give
a comprehensive account of utilization of ES and ESM in the removal
of inorganic substances. The removal of toxic metals from waste water
is a matter of great interest in the field of water pollution, which is a se-
rious cause of water degradation. Numerous metals such as chromium,
copper, cadmium, lead, mercury, arsenic, manganese, etc., are known to
be significantly toxic and in recent years their effective removal using
egg waste materials as adsorbents have been achieved. Moreover, re-
moval and recovery of precious metals like gold, silver, palladium plat-
inum etc. is also an important technological development which could
be easily achieved by ES and ESM adsorbents.
3.2.1. Natural ES & ESM as adsorbents
3.2.1.1. Actinides. Both Uranium and Thorium are important elements of
actinide series. They are naturally occurring, radioactive substances. As
far as their toxicity is concerned it is well documented in literature. On
breathing air containing uranium, its particles can easily enter into kid-
neys through bloodstream and can damage kidney cells. A high uranium
intake can cause acute kidney failure and death. Both U & Th are alpha
emitter and their isotopes pose severe radiation hazards towards
humans by developing cancer.
The first and the only report on the use of egg waste material as ad-
sorbent for the removal of an inorganic material appeared in 1999 in
which ESM was used for the removal of actinides from dilute waste ac-
tinide solution [58]. The adsorption of radioactive elements Uranium
and Thorium was investigated and time dependency, pH profile, ad-
sorption capacity were experimentally measured. ESM accumulated
uranium to a larger extent than thorium even from dilute aqueous solu-
tions through pH adjustment. ESM was found very effective for remov-
ing actinides from aqueous solutions and 60 and 240 mg adsorption of
Th(VI) and U(VI) respectively were achieved by 1 g of ES. The developed
method was proposed to be used in filtration technology.
3.2.1.2. Chromium. Chromium is widely used in industrial applications
such as electroplating, cement, steel, dyes, aluminum, leather tanning,
metal finishing etc. and unregulated disposal of effluents containing
chromium has led to contamination of soil and ground waters [59].
Though metallic chromium is not toxic but ionic forms of chromium,
which are present in industrial effluents, possess potential hazardous
effects on human health as well as animals. It is now well established
that hexavalent chromium Cr(VI) is much more toxic than trivalent
chromium Cr(III) [60]. Cr(VI) is carcinogenic and mutagenic to the living
organisms, and also considered much more hazardous than any other
heavy metal. According to environment protection agencies, the thresh-
old contaminant level of total chromium in public water systems is
100 ppb [61].
In the year 2005, Chojnacka [62] studied the biosorption of Cr(III)
from its aqueous solutions by ES and studied effect of various parame-
ters on the adsorption process. Crushed ES was found to possess almost
double adsorption capacity (21–160 mg/g) than activated carbon and
animal bones. The maximum experimentally determined adsorption
capacity 160 mg/g was obtained at low adsorbent concentration, 20 °C
and pH 5. ES was able to remove Cr(III) ions to a level lower than per-
mitted by environmental regulations, at a temperature of 40 °C, adsor-
bent concentration of 15 g/L and initial concentration of metal ions
100 mg/kg. Zou et al. [63] further improved this approach using ESM
381
for the sequential injection reductive bio-sorption of Cr(VI) and its spe-
ciation with detection by electrothermal atomic absorption spectrome-
try. Cr(VI) was adsorbed onto the surface of ESM with reduction to
Cr(III) ions through transient, unstable species of Cr(V) and Cr(IV),
while Cr(III) was virtually not retained. The experimental procedure in-
cludes the separation and pre concentration of Cr(VI) on ESM at pH 2
and its subsequent detection after elution, followed by conversion of
Cr(III) to Cr(VI) and then total chromium analysis. Cr(III) concentration
was finally obtained by subtraction. With a sampling volume of 1000 μl,
an enrichment factor of 13.3 was achieved. A linear range of 0.05–
1.25 μg/L for Cr (VI), along with a detection limit of 0.01 μg/L and a pre-
cision of 3.2% at the level of 0.5 μg/L, were obtained. Rajendran et al. [64]
explored the adsorption of Cr(VI) ions onto ES for various influencing
parameters and arrived at the conclusion that chromium removal
using waste material ES may be an eco-friendly, cost effective, time sav-
ing and more efficient than other conventional technologies to clean up
chromium contaminated sites. Daraei et al. [65] have worked extensive-
ly on the removal of Cr(VI) from waste water samples using ESM
through batch adsorption process. The ESM was characterized using
SEM, FTIR, and XRF analysis and its feasibility for adsorption of Cr(VI)
was evaluated. The experimentally gathered data was compared with
theoretical calculations based on central composite design (CCD) with
the variable parameters. The optimum conditions for maximum remov-
al of Cr(VI) were derived using CCD so that ESM can be utilized for max-
imum removal of metal ions. Based on the results of the CCD, the
maximum removal (81.47%) was achieved at temperature 20 °C,
pH 3.54, Cr(VI) ion concentration 5.0 mg/L, time 117.52 min, and dosage
3.78 g. In another report Daraei et al. [66] established that the adsorp-
tion of Cr(VI) ions onto ES occurs through ion exchange mechanism car-
bonate groups present on adsorbents play significant role, due to its
cation exchange properties. Authors also characterized ES and opti-
mized the parameters such as, pH, Cr(VI) ions concentration, amount
of ES, contact time, temperature for Cr(VI) removal from aqueous solu-
tions. The extraction efficiency of ES for the removal of Cr(VI) ions was
found higher than Cr(III) ions and approximately 93% of Cr(VI) ions
were removed at 25 °C at pH 5 in 90 min. Thermodynamic parameters
like, change in enthalpy (ΔH0), change in entropy (ΔS0), and change
in free energy (ΔG0) were calculated for the ongoing adsorption pro-
cess. Chromium adsorption kinetics was also found to be fitted in pseu-
do-first-order kinetic model. Quite recently, Kumaraswamy et al. [67]
improved this approach for the large scale application of ES for the re-
moval of Cr(VI) from waste water under industrial conditions. The de-
tailed performance analysis was carried out as function of various
operating parameters such as contact time, initial concentration, adsor-
bent dose, and particle size. The parameters affecting kinetics and equi-
librium of Cr(VI) adsorption onto ES powder were also determined very
precisely.
3.2.1.3. Copper. Copper is another toxic metal which poses potential
threat to the human health and environment, even at low concentra-
tions. Its toxicity is also called copperiedus, which is mainly due to ex-
cess of copper in the human body. Copperiedus can occur by eating
acidic foods cooked in uncoated copper cookwares or through exposure
to excess copper in drinking water or any other environmental resource.
It is also pertinent to note that copper present in organic form, like that
found in food, possesses beneficial micronutrient nature, while inorgan-
ic metallic copper is a toxic heavy metal and its toxicity symptoms are at
par with mercury and lead. The accumulation of copper in human body
causes skin, brain, pancreas and heart diseases [68]. The permissible
limit of copper is 2.5 mg/L in water. Wastewater from various industries,
such as plastic, metal finishing, electroplating, pigments, and mining
contains copper.
Carvalho et al. [69] performed a comparative study to evaluate the
adsorption efficacy of ES in treatment of simulated effluents and real in-
dustrial effluents to assess the adsorption capacity of ES powder in re-
moving toxic metal ions of copper and aluminum. Adsorption of
382 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
aluminum was studied in the wastewater effluent from an aluminum
anodizing plant. Results indicated that ES can remove several pollutants
from different types of aqueous systems, with great efficiency. The ES
adsorbent was found to possess better affinity for copper than for chlo-
ride and additionally, the results obtained for the adsorption of alumi-
num proved that ES works as an effective adsorbent in wastewater
from anodizing plants. Authors reported that the use of ES in real
waste water effluents does not require any change in operating condi-
tions of the adsorption procedures to apply this technique to real treat-
ment conditions.
3.2.1.4. Cadmium. Cadmium is a highly toxic metal with very low per-
missible exposure limit. It is widely used in electroplating industries
and in the manufacturing of cadmium containing batteries. Several in-
dustrial paints also contain Cadmium. “Cadmium Blues” is the common
name for the acute chromium exposure, which leads to flu-like symp-
toms including fever, cough, dryness, irritation of the nose and throat
and muscle pain. A long exposure to cadmium may lead to respiratory
problems, damage to the liver and renal failure. It is also a well known
carcinogen.
Characteristics of Cd ion removal by adsorption over ES have been
investigated for various parameters and adsorption was found to in-
crease with the increase in reaction time, the amount of ES, temperature
and pH. However, the amount of adsorption decreased with the in-
crease in the ES size. The paper also includes verification of various ad-
sorption isotherms and reaction kinetics [70]. Recently, Cano et al. [71]
researched extensively to investigate the mechanism and capacity of
adsorption of cadmium ions onto chicken ES. The ES was also character-
ized through XRD. The point of zero charge (PZC) of the ES was found to
be 11.4. The adsorption capacity of ES increased while raising the pH
from 4 to 6, this tendency was attributed to the electrostatic interaction
between the Cd2+ in solution and the surface of the ES. The adsorption
of Cd(II) occurred mainly onto the calcareous layer of the ES, but slightly
on the membrane layer. Authors reported that the adsorption of Cd(II)
was not reversible, and the main adsorption mechanisms were precipi-
tation and ion exchange. On the average, the contributions of the nonre-
versible and reversible mechanisms were 68% and 32%, respectively. An
important finding was that Cd(II) precipitated as (Cd/Ca)CO3 on the sur-
face of the ES during the adsorption of Cd(II). In a recent report [72], ad-
sorption of Cd was carried out over well grinded ES and maximum
monolayer adsorption capacity of 329 mg/g was achieved. Presence of
aragonite phase obtained due to phase transformation from calcite dur-
ing milling was considered the basic reason for such a high adsorption.
Adsorption was found to be obeyed through by Langmuir, Freundlich
and Dubinin–Radushkevich isotherms and second order rate kinetics
through intraparticle diffusion process. Another work by Aldaco et al.
[73] demonstrated utilization of ES as a source of calcium to improve
the adsorption capacities of commercial carbons to adsorb cadmium
from water along with nickel and zinc. The maximum adsorption capac-
ities of Cd2+, Ni2+, and Zn2+ at a temperature of 30 °C and pH 5 was im-
proved up to 15 times than the results obtained using the commercial
adsorbents without modification. The improvement of adsorbent per-
formance was related to the formation of calcium phosphate on the car-
bon surface and adsorption studies in binary metal solutions were also
performed to identify the competitive effects in multicomponent ad-
sorption, using calcium-modified carbons. The adsorption of Cd2 +,
Zn2+ and Ni2+ ions was also affected by the co-ion competition, espe-
cially at high metal concentrations and the metal uptake reduction
ranged from 0.1 to 77%.
3.2.1.5. Lead. Another metal present in industrial effluents is lead, which
is highly toxic and detrimental to environment because of its non biode-
gradable and persistent nature. It is widely used in petrol refining,
sulphuric acid manufacturing, manufacture of pigments, ceramics and
plastics, storage batteries etc., hence found in waste water arising
from these processes. The presence of lead in the human body is
commonly referred as “Lead poisoning” and severely affects central ner-
vous system of the human being, causing behavior disorders. Other
common symptoms of lead poisoning are confusion, headache, abdom-
inal pain, anemia, irritability and coma. Presence of lead in waste water
is well documented and a variety of approaches have been presented in
literature for the removal of lead from aqueous solutions.
A research was conducted to optimize the removal of lead from bat-
tery manufacturing waste water using hen ES and duck ES [74]. Natural
hen and duck ES have more protein fiber than boiled hen and duck ES,
which is responsible for higher binding of lead ions to their surface.
However, duck ES are more porous than hen ES which lead to higher
percentage removal of lead ions. As the main component of ES is calci-
um carbonate, its hydrolysis gives basic solution and the pH of the solu-
tion is further increased on increasing the amount of the adsorbent. The
optimum pH for lead removal was found 6. This study also concluded
that lead removal involved more than one type of mechanism i.e. ad-
sorption and precipitation. At higher dosage of ES, the final pH was N4
and solubility of lead decreased and consequently precipitation of lead
occurred as lead hydroxide complex. The final concentration of lead
was found lower than the waste water quality standards. Nearly
78.03% lead was removed at pH 6, contact time 90 min and 1.0 g of ad-
sorbent in 100 ml of battery manufacturing waste water. In a recent re-
port [75], a biosorbent derived from co-composting ES (30% w/w)
mixed with organic materials like potato peels, grass clipping, and rice
husk) was used for the adsorption of Pb(II) from its aqueous solutions.
The performance of the compost ES was also compared with matured
compost without ES and natural ES and about 43% increase in its sorp-
tion capacity was observed. Sorption kinetics and equilibrium data
were found fitted to pseudo-second-order and Langmuir models,
respectively.
3.2.1.6. Precious metals. Precious metals have wide range of applications
in various industries, agriculture and medicine, because of their specific
physical and chemical properties. These metals are very rare, mostly
occur in their elemental form and possess high economic values. Gold
(Au), Silver (Ag), Platinum (Pt) and Palladium (Pd) are internationally
recognized forms of currency under ISO 4217.
Ishikawa et al. in the year 2002 [76], evaluated ESM for the uptake
and recovery of gold ions from its solutions and electroplating waste
water. The ESM used was dried, grounded and sieved into various
sizes. Gold dicyanoaurate (I) and tetrachloroaurate (III) ions have
been adsorbed from waste water and recovered through desorption
with sodium hydroxide solutions. The adsorption capacities for Au(I)
and Au(III) over ESM were found as 147 and 618 mg/g, respectively. Se-
lective recovery of gold ions in presence of other ions was also investi-
gated in a flow through sorption column system and gold was found
to possess highest affinity for metal sorption among other metal ions.
The experimental findings suggested potential applications of ESM
biosorption column systems in recovery and refining of gold.
3.2.1.7. Light metals. Pettinato et al. [77] attempted to remove water pol-
luting metal ions Al3+, Fe2+ and Zn2+ by powdered ES and ESM and ap-
plied these as potential adsorbents to improve membrane biological
reactor (MBR) based technology used in sewage treatment process.
The development of technology was based on two steps. In the first
step concentration and size effect of the ES and ESM on fouling was con-
ducted to establish compatibility between the two processes. While, in
the second step quantitative analysis was made to evaluate adsorption
capacities of both the adsorbents by passing aqueous solution contain-
ing mixtures of Al3+, Fe2+ and Zn2+ through the reactor. Quite encour-
aging results have been found and it was concluded that application of
ES and ESM in MBR technology is a better option.
3.2.1.8. Fluorides. Fluoride is another toxic inorganic pollutant present in
nature, which pose significant health hazards to humans. A fluoride
containing drinking water is highly endemic and its excessive intake
 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
leads to the loss of calcium from the tooth matrix resulting thereby in-
curable aggravating cavity formation for entire life period [78]. Accord-
ing to the WHO recommendations maximum permissible limit for
fluoride in drinking water is 1.5 mg/L [79].
Bhaumik et al. [80] in the year 2012 explored the potential of ES
powder as an adsorbent for the removal of fluoride from aqueous solu-
tions and conducted equilibrium, kinetic and thermodynamic studies.
Fluoride adsorption was studied in a batch system where adsorption
was found to be pH dependent with maximum removal efficiency at
6.0 and energy of activation was found to be 45.98 kJ/mol by using Ar-
rhenius equation, indicating chemisorption nature of fluoride onto ES
powder. Authors concluded that adsorption of fluoride ions onto ES
powder is spontaneous and exothermic and ES powder can be used as
an effective, low cost adsorbent for fluoride removal from aqueous solu-
tions as well as ground water. In another study, an alumina supported
carbon composite material with exceptionally high defluoridation prop-
erty was developed from ES [81]. ES waste was used as calcium source
for the synthesis of ES composite that can be used as an adsorbent for
selective fluoride adsorption from aqueous solutions. The effect of vari-
ous synthesis parameters like ES – ESM ratio, aluminum loading, mixing
time and calcinations temperature were optimized. ES composite was
also characterized for elemental composition, morphology, functionali-
ty and textural properties. The adsorption capacity of ES composite was
37 mg/g at 303 K and it could be used over a wide range of pH 3–9. This
composite was more selective and efficient for fluoride removal and
proved to be a potential, indigenous and economic adsorbent for fluo-
ride removal.
3.2.2. Chemically modified ES & ESM as adsorbents
3.2.2.1. Chromium. In recent years, selective and enhanced metal ion ad-
sorption from waste water solutions was achieved by modified adsor-
bents. Guo et al. [82] prepared novel inorganic biocomposite Mg/Al-
−
CO2–3 and Mg/Al-Cl layered double hydroxide (LDH)/ESM membrane.
In this biocomposite, ESM served as a substrate and template to immo-
bilize the LDH, formed by an in-situ hydrothermal crystallization meth-
od. These biocomposites were then used as adsorbents for the removal
of Cr(VI) ions. The removal efficiency of ESM for removal of Cr (VI) ion
was increased from 80 to 90% at pH 4. ESM served as adsorbent as
well as support to uniformly disperse LDH and hence its adsorption per-
formance increased significantly. The composite membranes removed
Cr(VI) ion more efficiently than physical mixtures of LDH and ESM.
Higher percentage of Cr(VI) ion was extracted at pH 5 using ES powder,
however the pH values reported for highest extraction were 2.0 and 5.1
for ESM and CO2– 3 loaded LDH–ESM, respectively. The adsorption ability
of LDH in composite membrane was further enhanced by the develop-
ment of Cl− LDH/ESM composite membrane through an anion ex-
change treatment method well characterized through SEM and XRD
patterns. The method was found highly effective for extracting metal
at natural pH of the solution. The maximum percentage removal of
Cr(VI) was at pH 4 and at a temperature of 20 °C because at greater
pH the fat from the adsorbent is dissolved to the water, which resulted
into the turbidity, leading thereby poor adsorption of Cr(VI) ions on the
ESM surface. In an advanced research, Liu and Huang [83] developed a
novel bioadsorbent for adsorption and detoxification of Cr(VI) from
water. The polyethyleneimine (PEI) functionalized biosorbent using an
ESM as a model was synthesized, based on the cross linking reaction be-
tween aldehydes in glutaraldehyde, and the functional groups such as
amides and amines present in ESM. The prepared biosorbent interacted
strongly with Cr(VI) and the dynamic uptake capacity of the PEI–ESM
increased by nearly 105%. The maximum equilibrium adsorption capac-
ity for Cr(VI) was found to be about 160 mg/g with an initial pH of 3.0
after this modification. Raman spectroscopy and X-ray photoelectron
spectroscopic analysis, performed on the prepared biosorbent before
and after Cr(VI) adsorption suggested that some of adsorbed Cr(VI) an-
ions were reduced to Cr(III) in Cr2O3 or Cr(OH)3 during the sorption
383
process, hence PEI–ESM bioadsorbent could detoxify Cr(VI) through
its reduction to less toxic Cr(III) ions. In a most recent publication,
Chen et al. [84] used chemically modified ES biosorbent to remove phos-
phate and Cr(VI). The chemical modification of ES surface was made by
using α-FeOOH (F-ES) and ascertained through EDS, XRD and FTIR anal-
yses. It was also observed that by increasing the sorption sites through
modification adsorption of phosphate and Cr(VI) could be enhanced.
The unmodified ES adsorbed 89.74 and 11.81 mg/g phosphate and
Cr(VI), while F-ES increased it to 248.73 and 41.57 mg/g, respectively.
Kinetics of the adsorption was also monitored and the kinetics data
were found fit with pseudo-first and second order kinetics equations.
Richie kinetics model was also applied and it was found that the adsorp-
tion on ES was controlled by multiple mechanisms.
3.2.2.2. Copper. In the year 2010, Ahmad et al. [85] developed an iron
oxide coated ES powder for effective removal of Cu ions from aqueous
solutions. The adsorption characteristics of iron oxide coated ES powder
(IOESP) were systematically studied in batch as a function of contact
time, pH, metal ion concentration, and temperature. The IOESP was pre-
pared by chemical precipitation of FeSO4·7H2O onto hen ES powder. It
exhibited a remarkably enhanced adsorption capacity for Cu2 + than
the pure iron oxide and ES powder. The equilibrium data fitted well to
Freundlich isotherm, which suggested heterogeneity in the adsorption
sites. Regeneration of metal ion were performed using HCl, EDTA,
HCOOH and NaOH as eluting agent from saturated IOESP and the max-
imum regeneration was observed with HCl. The adsorption of Cu2+ was
found to increase in the presence of anionic surfactant, while cationic
surfactant showed no significant change in adsorption capacities. Ther-
modynamic parameters indicated that the adsorption of Cu2 + onto
IOESP was feasible, spontaneous, and exothermic. The maximum mono-
layer adsorption capacity of this modified ES powder for Cu2+ removal
was found 44.843 mg/g.
3.2.2.3. Arsenic. Arsenic is another highly toxic pollutant present in in-
dustrial effluents related to pesticides production, wood preservatives,
glassware production, electronics industries etc. [86,87]. The inorganic
form of Arsenic is considered more toxic than organic form i.e.
aresenites present in drinking water in the trivalent form are more
toxic than organic arsenates of pentavalent form [88]. Arsenic have
caused a potential threat to human health owing to its carcinogenic ef-
fects on lungs, kidneys, liver, bladder, hematopoietic system, and the
central nervous system, cardiovascular diseases, and dermal changes
[89]. A long exposure to arsenic may cause deficiency of vitamin A caus-
ing thereby heart diseases and night blindness.
Considering the potential toxicity of arsenic, Zhang et al. [90] con-
ducted a study to utilize ESM as SPE adsorbent for the retention of arse-
nic in combination with hydride generation atomic fluorescence
spectrometry (HG-AFS). It was reported that under the optimal condi-
tions, As(V) could be easily extracted by the ESM packed cartridge and
the breakthrough adsorption capacity was found to be 3.9 μg/g. The fa-
vorable limit of detection for As(V) was found to be 0.001 μg/L with an
enrichment factor of 33.3, and the relative standard deviation was 2.1%
for 0.6 μg/L of As. The proposed method was also successfully applied for
the analysis of As(V) in aqueous environmental samples. In another
study, Chen et al. [91] demonstrated the most interesting approach for
the development of green biosorbent through modification of the sur-
face of ESM focusing on certain functional groups for ultra-high selec-
tive uptake of As(V) against As(III) with detection by hydride
generation atomic fluorescence spectrometry. The presence of carbox-
ylic groups on ESM surface restricted the arsenic adsorption, hence,
ESM was modified by esterification with methanol and the methyl es-
terified ESM (MESM) was explored for adsorption of Arsenic from
waste water samples. As a novel green adsorbent material, MESM ex-
hibited 200 fold improvements on adsorption capacity of arsenate
with respect to bare ESM. It presented an ultra-high selectivity of
256:1 towards arsenate against arsenite. At pH 6, 100% adsorption
384 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
efficiency was achieved for 2 μg/L As(V) by 10 mg MESM, while no ad-
sorption of As(III) was observed. This provided great potential for selec-
tive uptake of arsenate in the presence of arsenite. Thus total inorganic
arsenic could be removed by converting As(III) to As(V) and following
the same adsorption process. The results were confirmed by graphite
furnace atomic absorption spectrometry and spiking recovery. Authors
concluded that MESM provided a practical approach for the speciation
of inorganic arsenic species in real waste water samples.
3.2.2.4. Mercury. Mercury is one of the most toxic heavy metals, which is
dangerous to humans in elemental as well as ionic forms. The elemental
form of mercury can exists in vapor and liquid states and exposure of
both the states is fatal for the humans and can cause blocking of blood
vessels. Other toxic effects of the metal include damage to the brain, kid-
neys and lungs. Sensory impairment, disturbed sensation and lack of co-
ordination are common symptoms of mercury poisoning.
Cheng et al. [92] in the year 2010 developed a thiol functionalized
ESM through esterification between thioglycolic acid and oxygen-con-
taining functional groups. The potential biosorbent thus formed was
used for the removal of toxic mercury in wastewater solutions. The
modified ESM greatly enhanced the adsorption capacity for Hg2+ and
the maximum capacity was increased N 3-fold in comparison with the
unmodified ESM, from 19.4 mg/g to 71.9 mg/g. This novel thiol-func-
tionalized ESM was able to remove and recover mercury even from
very low concentration of mercury from wastewaters. This approach
was further improved in the year 2013 by Wang et al. [93], who studied
adsorption of mercury along with several other toxic heavy metal ions
from aqueous solutions on ESM functionalized with ammonium
thioglycolate. Thiol functionalization was based on the reduction of di-
sulfide bonds in ESM by ammonium thioglycolate. Authors character-
ized thiol-functionalized ESM and investigated its application as an
adsorbent for the removal of Hg(II), Cr(VI), Cu(II), Pb(II), Cd(II), and
Ag(I) from waste water samples. The experimental results revealed
that the adsorption abilities of the thiol-functionalized ESM towards
Hg(II), Cr(VI), Cu(II), Pb(II), Cd(II), and Ag(I) improved 5.5, 1.6, 7.7,
12.4, 12.7, and 21.1 fold, respectively, compared with that of the ESM.
The developed membrane was used as column packing material to fab-
ricate column for wastewater purification.
3.2.2.5. Gold. In another novel development, Shoji et al. [94] proposed a
bead type adsorbent made from chitosan and ESM with improved ad-
sorption efficiency for precious metal ions. The ESM-conjugated chito-
san beads were examined for recovery of gold ions from dilute
aqueous solutions as well as selective adsorption from mixtures of
metal ions. Based on the experimental findings, ESM conjugated chito-
san beads adsorbed gold and copper up to 100% and 2% respectively
from mixture of gold and copper ions. Authors presented a new prom-
ising modified adsorbent for the selective uptake of gold ions. In the
year 2007, Goto [95] widely researched protein rich biomass, a
byproduct in the food and agricultural industries, for the selective re-
covery of precious metal ions from industrial waste water without
extra emissions of carbon dioxide. Mechanistic aspects of the metal
ions adsorption onto protein rich biomass were taken into account
and selective recovery of the targeted metal ions due to their specific in-
teraction with the functional groups present in protein structures was
also demonstrated. A comparative study was conducted between puri-
fied proteins and ESM (90% protein) for the uptake of gold and platinum
ions and the adsorption selectivity of protein rich biomass was found
very similar to that of purified proteins. The precious metal ions bound-
ed to the proteins were recovered by nitro hydrochloric acid after char-
ring the metal bound biomass. Au3 + and Pd2 + were successfully
recovered from a metal refining solution and a metal plating waste
using the biomass. An environmental friendly recycling system was pro-
posed for precious metal ions using protein-rich biomass with an ex-
tremely high loading potential 250 g/kg for gold ions.
3.3. Applications of ESM nanoparticles
In the last 2–3 years some of the adsorption abilities of particularly
ESM nanoparticles have been explored to derive certain typical and use-
ful applications.
One of the researches includes the use of ESM nanoparticles in Lith-
ium – Sulphur cell to improve its efficiency. Chung, and Manthiram [96]
claimed that carbonized ESM (CESM) powder, with abundant micro
pores and high porosity, when embedded within conventional Sulphur
cathodes (CESM-S cathodes) as a polysulfide (PS) adsorbent, provided
improved performance, efficiency and long-term cyclability to Li\\S
battery. Thus polysulfide absorbent for highly stable and reversible
Li\\S Cells were developed from a natural ESM. In another research
published in the year 2015, protein cavities present in ESM were used
as natural biotemplate for the growth of nanoparticles [97]. Fibrous
oxide ceramics were prepared by wet impregnation of biological tem-
plate with water solution of cerium nitrate. Unique bio-morphic CeO2
microstructures with interwoven networks were synthesized and char-
acterized by scanning electron microscope (SEM) and X-ray diffraction
(XRD), whereas low-temperature nitrogen adsorption (BET) method
was used in order to characterize porous properties. Pramanik et al.
[98] introduced water soluble blue-emitting Au\\Ag alloy nanoparticles
and fluorescent solid platforms for the removal of dyes from water by an
ESM-induced reduction process. Chicken ESM, was used to prepare
nano clusters of gold (Au), silver (Ag) and their bimetallic (Au\\Ag)
alloy at room temperature, without using any reducing agent or cata-
lyst. The Au and Au\\Ag alloy clusters were highly fluorescent and ex-
hibited intense blue emission around 435 ± 5 and 440 ± 5 nm,
respectively. These metal clusters immobilized inexpensive ESMs have
also been explored in removing organic dyes from water. Authors re-
ported that ESM can be converted into an effective platform for water
purification because of its strong adsorption of the dye molecules in
the presence of the metal particles. This process has the dual advantages
of utilizing an inexpensive, abundant and eco-friendly food waste for in
situ reduction and formation of metal nanoparticles and the utilization
of the same as an effective platform for the removal of anionic dyes
from waste water.
3.4. Carbonate hydroxylapatite as adsorbent
Carbonate hydroxylapatite (CHAP) is a nanostructured material,
which is synthesized by using ES waste as a raw material. CHAP is con-
sidered as expensive material because of the use of high purity reagents
in its synthesis [99]. It is indeed a calcium phosphate ceramic material,
which possesses extensive biomedical applications. It is also used as po-
tential adsorbent and recently has been utilized for the removal of lead
and cadmium ions from waste water. Synthetic carbonate HAP (CHAP)
has higher efficiency in the removal of heavy metals, but their adsorp-
tion characteristics were not investigated probably due to their high
cost of preparation [100,101].
Lead ions have a relatively high affinity for CHAPs. Liao et al. [102] in-
vestigated the kinetics of removal of lead ions by CHAP derived from ES
waste. The effect of lead concentration, contact time, pH was observed
in batch experiments. The adsorption of lead ions onto CHAP involved
two types of interactions, one ion exchange between lead and calcium
ions and another complexation of lead ions by CHAP. Increase in pH of
the solution decreased the net positive charge on CHAP and hence fa-
vored complexation mechanism. The adsorption procedure favored
pseudo second order kinetic model having higher value of regression
coefficient (R2 = 0.9991) and Langmuir adsorption model with regres-
sion coefficient value of 0.9995 as compared to 0.8002 of Freundlich
model. Maximum lead ion concentration that could be adsorbed onto
CHAP derived from ES is 101 mg/g, which is far greater than ES adsorp-
tion capacity for lead ions, however the calculated monolayer adsorp-
tion capacity was 94.3 mg/g at pH 6 with metal ion concentration of
10–500 mg/L. This work has established CHAP extracted from ES
 A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387
waste as efficient adsorbent for lead removal. On comparing the results
of previous workers [103–106], CHAP possessed higher extraction effi-
ciency than calcium HAP (85 mg/g), activated carbon (31.20 mg/g)
and wheat bran (87 mg/g). In another development, CHAP derived
from ES waste was characterized for physical and chemical properties
minimizing contaminants for its potential use in lead removal [107].
The derived HAP was heated at 600 °C for 3 h and a remarkable increase
in adsorption capacity of CHAP was observed after calcinations. The re-
moval efficiency of lead ions by CHAP reached to 99.78% with initial con-
centration of 200 mg/L, pH 3 and adsorbent 1 g/L. The mechanism of
lead removal at low pH and low lead concentration involved the disso-
lution of CHAP and precipitation of HAP, however at higher concentra-
tions adsorption of lead ions and ion exchange was involved. This
extensive experimental study revealed that CHAPs derived from ES
waste were potent adsorbents for lead removal with adsorption capac-
ity even higher than hydroxyapatite/polyurethane composite foams
(150 mg/g).
Zheng et al. [108] in the year 2007, proposed a new process for the
synthesis of carbonate hydroxylapatite (CHAP) using and explored the
possibility of adsorption of Cu(II) and Cd(II) ions from aqueous solu-
tions. The adsorption process was optimized and the results revealed
that the removal efficiency of Cu(II) and Cd(II) by CHAP could reach
93.17 and 94% respectively, at the initial Cu(II) concentration 60 mg/L
and Cd(II) 80 mg/L and the liquid/solid ratio was 2.5 g/L. The maximum
adsorption capacities for CHAP prepared by ES waste were 142.86 mg/g
and 111.1 mg/g for Cu(II) and Cd(II), respectively, which are much
higher than previous findings. Authors suggested that the mechanism
of metal ions removal by CHAP included ion exchange/adsorption and
precipitation.
4. Conclusions
Bird eggs have interesting anatomy and their waste materials, ES
and ESM can be utilized for various purposes, including adsorption of
various pollutants. The literature review presented above clearly indi-
cates that the adsorption abilities of ES and ESM have been smartly
exploited by various researchers. A careful inspection of the published
articles confirms that pioneer in utilizing egg waste have been Ishikawa
and his research group, who first removed actinides from the wastewa-
ter using ESM as adsorbent in the year 1999. Among the inorganic metal
ions, Cd2+ is the first ion, which has been removed from waste water in
the years 2000 and 2001. Chronology of the work shows that removal of
gold and lead ions was achieved in the year 2002, only gold ions in the
year 2004 and Cr(III), Pb(II) and As(III) ions in the year 2005. As far as
organic substances are concerned, the first report was published in the
year 2006 on the adsorption of reactive dye over ES and ESM. After
year 2006, research involving ES and ESM as adsorbent, took a new di-
mension and large number of research papers on this subject matter ap-
peared in various journals. Thus in last almost 10 years, maximum use of
ES and ESM as adsorbents has been done on the removal of toxic heavy
metal ions and hazardous dyes. There are only limited numbers of re-
search papers available on the removal of morphine, phenol, malathion,
humic acid, alkyl benzene sulphonates, PAHs, actinides and fluorides.
After initial work on the use of natural ES and ESM as adsorbents, in
the year 2010 attention shifted to the chemical modification of ES and
ESM. This alteration in the surface structure of ES and ESM provided bet-
ter prospects in the removal of organic and inorganic chemicals with
specificity and quantity. Hence, several methods have been developed
where chemically modified ES and ESM have been used for the removal
of specific chemical(s) e.g. metal ion, from the wastewater containing
mixture of pollutants. Chemical modification also improved the kinetics
of removal and fastened the process of eradication of pollutants. Since
natural and chemically modified ES and ESM have been mainly used
for the removal of toxic heavy metal ions and hazardous dyes from
wastewater, there is still vast scope to utilize these adsorbents to scav-
enge variety of pollutants like pharmaceutics, pesticides, surfactants,
385
radioactive substances, lanthanides, etc. Captivatingly, in last two
years, uses of ESM nanoparticle adsorbent in fuel cell, bio-templates
and water purifier have elevated the importance of ES and ESM. Though
use of CHAP obtained from egg shell waste is not very cost effective but
the removal of Pb and Cd ions using nanostructured CHAP is highly
efficient.
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