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

Article  in  Journal of Molecular Liquids · November 2016


DOI: 10.1016/j.molliq.2016.08.065

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Journal of Molecular Liquids 223 (2016) 376–387

Contents lists available at ScienceDirect

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) 376–387 377

1. Introduction section incorporates the conclusions drawn on the research carried


out so far in this area and future challenges. The second section mainly
Removal of toxic pollutants from the industrial, municipal and other presents anatomy of egg, which includes detailed description of egg, ES
waste solutions is the cause of global concern. Presence of toxic and ESM and their chemical compositions. The third section includes
chemicals in the environment poses significant environmental hazards, the highlights of the work carried out by taking ES and ESM as adsor-
as these chemicals ultimately reach and accumulate in animal and bents. For the benefit of readers this section is further divided into
human tissues. In order to minimize this threat several physico-chemi- three sub sections, which present literature review of removal of organ-
cal methods, such as reverse osmosis and ultrafiltration, oxidation/re- ic and inorganic pollutants using ES and ESM and some other novel ap-
duction, precipitation, adsorption electrodialysis etc. have been plications of ES and ESM, respectively. In all the three sub-sections, the
employed [1–4]. Among all these methods, adsorption has gained tre- highlights of available literature review are placed quite systematically
mendous importance due to its high efficacy, cost-effectiveness, versa- in different categories and types of pollutants. For example, use of ES
tility and easy handling [5]. Unlike many other degradation methods, and ESM for the removal of organic compounds like dyes (acidic/
adsorption does not leave behind any toxic intermediate(s) or basic/azo and styryl pyridinium dyes), pharmaceutics (morphine), phe-
byproduct(s) of particularly complex organic pollutants. Moreover, as nol, pesticide (malathion) and humic acid is presented first followed by
globally environmental standards are getting more and more stringent, the role of chemically modified ES and ESM for the removal of organic
technical applicability and financially viability have become the key fac- compounds like anionic dyes, surfactants (linear alkyl benzene
tors, while selecting a suitable treatment process. Conventional sulphonates) and polycyclic aromatic hydrocarbons (PAHs). Similarly
physico-chemical treatment methods also involve careful disposal, in- in the second subsection description on the application of ES and ESM
complete removal, requirement of high energy and costly chemicals as adsorbents for the removal of inorganic pollutants like Cr, Cu, Cd,
and reagents, which escalates the treatment cost, reduces the efficiency Pb and precious metals, actinides and fluorides is presented prior to por-
of the process and produce other toxic waste products [1,2]. Therefore trayal of research on the adsorption over chemically modified ES and
adsorption is the final choice, which has been universally accepted by ESM for the removal of toxic inorganic pollutants like Cr, Cu, Pb, As,
the world environmentalists for the disposal of hazardous and toxic in- Hg and Au. The third subsection is devoted to some recent interesting
organic as well as organic pollutants present in various effluents. researches, where ESM nanoparticles have been utilized for various
One of the key factors associated with the adsorption process is the other interesting (though limited) applications like fabrication of fuel
selection of adsorbent, which ultimately decides the economics, effi- cell, bio-templates and water purifier. Overall 108 research articles
ciency and versatility of the process. The first documented adsorption have been included in this literature review. The review article is a
has been carried out by employing charcoal as adsorbent [6]. Over sev- thoughtful attempt of authors to present up-to-date information on
eral decades, with availability of very limited choices of adsorbents, ‘ac- the subject matter. The article meticulously describes future prospects
tivated carbon’ despite an expensive material has been widely used as and challenges associated with egg waste materials and presents sys-
adsorbent for the removal of various pollutants. Of course high cost of tematic growth of research in this area.
activated charcoal restricted its applications and therefore over the
years the focus of research has been shifted to replace commercially 2. Anatomy of egg
available activated charcoal by suitable low cost alternatives, preferably
waste materials [1,2]. As far as substitute adsorbents are concerned, as- Birds, reptiles and fishes are those living species which produce a
sociated history has been summarized in several books, reviews and hard shelled egg to develop outside female body. Every egg is self
monographs [7–14]. In nut shell it can be narrated that at least past contained and does not require any external nutrient. ‘Oology’, the sci-
two decades have witnessed emergence of large number of low cost ad- ence of anatomy and physiology of eggs, descries that every egg consists
sorbents and biosorbents derived from industrial, agricultural and other of mainly four basic structures, a protective layer (ES), a membrane as-
natural waste materials as potential adsorbents for scavenging different sociated with shell, an egg white (albumen) and yolk (vitellus). Fig. 1
varieties of toxic pollutants [7–14]. gives an illustrative view of the framework of the egg. The usefulness
With the advent of use of waste materials as adsorbents several us- of the egg is mainly due to protein and nutrients present in liquid
able bio-wastes obtained from humans, birds and animals like hairs, state as egg white and egg yolk, while the solid protective layer (ES)
feather, nails, horns etc. have been used as potential adsorbents for and its associated membrane (ESM) are usually thrown in the waste
the removal of inorganic and organic compounds [15–18]. Egg shell basket.
(ES) and egg shell membranes (ESMs) are waste materials emerging
out in large quantities from sources such as poultries, homes, restau- 2.1. Egg shell (ES)
rants, bakeries and food manufacturing units [19]. Out of these sources,
bakeries and food industry gives largest chunk of ES and ESM and their The hard protective cover of the egg, the ES, consists of three layers,
disposal is always been a challenge to the concerned authorities [20]. the outermost layer, ‘Cuticle’, beneath to cuticle is the calcium carbonate
The cost associated with egg waste disposal is expected to increase layer, ‘Testa’, and finally the innermost layer, ‘Mammillary layer’. Cuticle
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 Eggshell
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 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- interact with some chemical species present in the albumen. Due to
tect embryo from bacterial infections and regulate evaporation of mois- the presence of various functional groups, ESM acts as a potential
ture. Testa provides calcium to the growing egg and helps in coloration adsorbent.
of egg. However, Mammillary layer gives foundation to the testa and
makes direct contact with the shell membranes. 3. Review of literature
Both Cuticle and Mammillary layers together form a matrix com-
posed of protein fibers, which is bonded to calcite (calcium carbonate) Surface analysis of ES and ESM indicates that these are porous mate-
crystal. The two layers are also constructed in such a manner that rials and therefore can also be utilized as effective adsorbents. Thus use
there are numerous circular openings (pores), which allow transpira- of ES and ESM as adsorbents serves two purposes, as cost effective and
tion of water and gaseous exchanges, throughout the shell. Each ES necessitous removal of hazardous chemicals and lessening of the
has been estimated to contain between 7000 and 17,000 pores [24]. landfill's loads. Adsorption is a well established eco-friendly and clean
The outer surface of the ES is covered with a mucin protein, which technology, whereas egg waste materials have been utilized as effective
acts as a soluble plug for the pores in the shell. alternatives to the existing adsorbents. Thus over the last one decade
Different birds have different thicknesses of the shell of their egg. Os- egg waste materials, particularly ES and ESM have been used in waste-
trich, chickens, ducks, etc. have very thick ES, while small birds like water treatment to remove organic and inorganic hazardous sub-
hummingbirds, sparrows, finches, etc. generally have very thin ES. It is stances. In recent years, chemically modified adsorbents have
speculated that thickness of the ES is due to absorption of more calcium attracted considerable attention. Several attempts have been made to
from the shell during the growth of an egg. The size of the egg depends chemically modify ES and ESM to achieve either selective or/and im-
upon the size of the yolk, while shape of an egg resembles a ‘Prolate proved adsorption. With the invention of nanoparticles as superior
Spheroid’ with one end larger than the other and cylindrical symmetry technology, ESM nanoparticles have also emerged as useful adsorbent
along the long axis. There are few species like owls, which lay very material and few interesting researches have been witnessed very re-
round eggs on the other hand fast-flying, stream-lined birds like swifts cently. All these available reports on the use of ES and ESM as adsor-
and swallows lay long and elliptical eggs. Interestingly, the color of the bents are summarized in the following paragraphs.
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 3.1. Adsorptive removal of organic pollutants
during formation of egg in oviduct. Apart from common white some at-
tractive egg colors are shiny, emerald green, blue, greenish-black, Industrial effluents contain variety of organic pollutants such as
creamy beige, brownish-orange, brown with black markings and eggs dyes, pesticides, aromatic compounds (phenol), detergents, humic
with red tint. It is presumed that egg color and markings help the bird acid etc. and this is mainly due to extensive use of organic chemicals
to camouflage and protect the eggs from their enemies. in many industries such as food processing, cosmetics, paper, textile,
fertilizer etc. A large number of these organic substances are highly
2.2. Eggshell membrane (ESM) toxic and pose serious health hazard to aquatic living organisms, ani-
mals and humans. The fact that many of such organic substances are
There are two membranes which lie directly beneath the shell and carcinogenic and mutagenic in nature and severely effect human life
these are conveniently called inner and outer shell membranes. The cannot be neglected. Keeping these in view it is highly essential to erad-
outer shell membrane remains adhered to the mammillary layer of icate these organic substances from waste water before it is discharged
the shell, while inner shell membrane surrounds the liquid of the egg. to water courses [30] and adsorption has been found most effective and
It is also pertinent to note that these two membranes separate at the versatile in this task. In the hunt of economic adsorbent, egg waste ma-
larger end of the egg and create a space between them called as ‘Air terials, particularly ES and ESM have been found excellent scavengers
Cell’. This air cell is formed due to contraction and cooling of egg con- for the organic compounds such as dyes, surfactants, phenols, humic
tents after it is laid by the bird. The ESM is a clear thin film lining the acid and pesticides.
ES and visible on peeling the boiled egg.
ESM possesses porous and fibril structure, which is responsible for 3.1.1. Natural ES and ESM as adsorbents
its good adsorption properties. It is an amorphous natural biomaterial
with an intricate lattice of stable and water insoluble fibers [25]. It is 3.1.1.1. Organic dyes. Acidic dyes are one of the most important dyes
usually light pink double layered membrane and each of these mem- which are widely used in the textile dyeing industries. They possess
branes is composed of protein fiber that is arranged so as to form a high solubility in water and strong affinity towards amphoteric fibers
semi-permeable membrane. The total thickness of these two mem- like wool, acrylic, silk etc. Due to their high solubility in water their re-
branes is about 100 μm. moval by common physico-chemical methods is difficult, while adsorp-
tion over ES, ESM and ES–ESM mixture has proved its ability to remove
2.3. Chemical composition of ES & ESM toxic acidic dyes effectively and efficiently. The adsorption characteris-
tics of C.I. Reactive Yellow 205, an acidic dye, showed that ES and ESM
Major constituents of the ES are carbonates, sulphates and phos- are useful materials for the removal of Reactive Yellow 205 dye from in-
phates of calcium and magnesium and organic matter. Traces of Na, K, dustrial waste water [31]. Adsorption affinity of the dye is found to de-
Mn, Fe, Cu, and Sr metals are also present in ES [26]. The density of ES pend upon the nature of charge of the adsorbent, hence on the pH of the
is about 2.53 g/cm3, which is significantly larger than that of ESM solution. Within initial range of concentration (20–100 mg/L) over 72 to
(1.358 g/cm3). Major Constituents of ES are calcium carbonate (94%), 99% of the dye was adsorbed at equilibrium. The adsorption capacities of
organic matter (4%) calcium phosphate 1% and magnesium carbonate ES, ESM and ES–ESM mixture were found to be 32, 34, and 185 mg/g, re-
(1%). ESM possesses nearly 60% protein {collagen (35%), Glucosamine spectively, proving thereby greater adsorption affinity of ES and ESM
(10%), chondroitin (9%) and hyaluronic acid (5%)} along with other in- mixture for the Reactive Yellow 205 dye than ES or ESM separately. In
organic components like Ca, Mg, Si, Zn, etc. in smaller quantities [27– two reports published in the years 2006 and 2008 Arami and coworkers
29]. [32,33] established ESM as natural and eco-friendly adsorbent material
The membrane surface bears positively charged sites produced by for the removal of few acidic dyes. In the first report [32] adsorption ca-
basic side chains of amino acids. It has a very high surface area with spe- pabilities of ESM to remove dyes Direct Red 80 and Acid Blue 25 from
cial functional groups such as hydroxyl (−OH), thiol (−SH), carboxyl their aqueous solutions were established through Langmuir, Freundlich,
(− COOH), amino (− NH2), amide (− CONH2) etc., which strongly BET, Redlich-Peterson and Tempkin adsorption isotherm equations and
A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387 379

it was found that adsorption of both the dyes onto ESM perfectly obeys 30 min equilibrium time. Pseudo second order kinetic model was
Redlich-Peterson adsorption isotherm. The pH studies reveal that the found to describe the ongoing adsorption process.
adsorption capacities of both the anionic dyes onto ESM increased Literature survey reveals that very limited work has been done so far
with decreasing pH of the solution, while for desorption reverse trend to remove azo dyes using egg waste materials as adsorbents. Liu ana-
was observed. It was found that in the basic medium at pH 12, maxi- lyzed the adsorption and decolorization of water-soluble azo dye
mum desorption (≥81.8%) was achieved for both dyes, it is due to signif- Eriochrome Black T [39] and Eosin [40] on ESM and achieved about
icantly high electrostatic repulsion between the negatively charged 95% of removal of Eriochrome Black T from its acidic solution and almost
surface of the adsorbent and anionic dyes, which resulted into high de- same amount of removal for Eosin from its monohydrate solution.
sorption rate of dyes. In another study Arami et al. [33] carried out ad- Styryl pyridinium dyes have a large number of industrial applica-
sorption of dyes Acid Red 14 and Acid Blue 92 (AB92) onto the tions like in photoresists, electrophoresis, in the production of
microporous and mesoporous ESM in aqueous solutions in the batch photoconducting layers, dying of paper etc. [41]. It is interesting to
systems. Detailed research studies include effect of initial dye concen- note that ES particles potentially adsorb even the traces of styryl
tration, pH, contact time, particle size and biosorbent dosage on the ad- pyridinium dyes from their aqueous solutions. As reported by Guru
sorption of the undertaken dyes over ESM at 20 ± 1 °C temperature. and Dash [42], nearly 20% of the typical cyanine dye styryl pyridinium
Paper also includes characterization of ESM by using Fourier transform was removed from its aqueous solution at 25 °C, 200 mg of ES particle
infrared (FT-IR) and scanning electron microscopy (SEM). The surface in fixed dye concentration of 2 × 10−5 M. Authors further studied the
area of ESM was also evaluated and found to be 2.2098 m2/g. The pseu- effect of kosmotrophs and chaotrophs on the adsorption process of
do-first-order, pseudo-second-order kinetics and the intra-particle dif- styryl pyridinium dye by ES particles. Hydrogen bonded structure of
fusion models were used to describe the kinetics data. Like previous aqueous medium was found to affect the extent of adsorption signifi-
report [33], equilibrium adsorption isotherms were analyzed for Lang- cantly. The extent of adsorption of styryl pyridinium dye capable of hy-
muir, Freundlich and Redlich–Peterson adsorption models and the ex- drogen bonding with water molecules in solution increases with
perimental data were found well fit on Redlich–Peterson adsorption addition of kosmotroph (water structure making salt) such as sodium
isotherm model. As far as desorption is concerned at pH 12 maximum chloride and decreases on addition of chaotroph such as potassium
desorption, around 89.6% was achieved for Acid Red 14 and 82.8% for chloride and ammonium thiocyanate (water structure breaking salt).
Acid Blue 92 in their aqueous solutions. In another work, Tsai et al. Kosmotrophs enables water molecules bound with each other through
[34] studied detailed adsorption characteristics of Acid Orange 51 onto extensive hydrogen bonding, which changes the solvation pattern of
ES particles and compared the data with the adsorption of basic dye the dye molecules leaving them free to adsorb on the surface of ES par-
Methylene Blue. It was found that at neutral pH, the dye Acid Orange ticles. If the dye is unable to form hydrogen bonds with water molecules
51 possess better adsorption ability over ES (about 60%) than Methy- then the addition of kosmotroph or chaotroph is not so effective in
lene Blue (about 10%). The feasibility of ES for the removal of another changing the solvation pattern of the dye. However a marked increase
acidic dye, Reactive Red 123 from its aqueous solutions has also been in- in adsorption capacity for the dye is due to partial neutralization of
vestigated by Ehrampoush et al. [35]. Experimental data were analyzed the surface of adsorbent leading to reduction in repulsive forces
with Langmuir, Freundlich and Temkin adsorption isotherm models and among adsorbate and adsorbent.
found in good concordance with Langmuir and Freundlich models The anthraquinone dyes are also called vat dyes and well known for
(R2 N 0.90). Interestingly, increase in ES dosage and the solution temper- their brilliant colors. Though these dyes possess poor solubility in water
ature beyond 45 °C decreases the adsorbed dye per gram of adsorbent, but can dissolve after the treatment with a reducing agent, usually sodi-
however, increase of pH of solution up to 9 results into improvement um hydrosulfite. Attempts have also been made to remove anthraqui-
of the dye adsorption over ES. The kinetic studies revealed that the ad- none class of dyes, alizarin (1,2-dihydroxyanthraquinone) and 2-
sorption of Reactive Red 123 was rapid and obeyed pseudo-second aminoanthraquinone using ES as an adsorbent [43]. Preliminary studies
order rate kinetics with the kinetic constant of 0.02 g/mg·min. were made and optimum conditions for the dyes removal were
Basic dyes are popular due to their low cost, wide shade range, established through pH, concentration, temperature, contact time and
brightness of colors, moderate substantivity and high tinctorial ES dosage studies and maximum adsorption was observed at pH 7 in
strength. Methylene Blue is one of the most important basic dyes, 30 min. The amount of dye uptake was also found to increase with in-
which is widely used in textile dyeing industries as well as in analytical creasing dye concentration and decrease with increasing amount of ad-
laboratories. It is a well known fungicide, which is used for the protec- sorbent. The data were found fit in the Langmuir and Freundlich
tion of aquatic animals particularly fishes. One of the early attempts to adsorption isotherm models and it was concluded that powdered ES is
remove Methylene Blue by adsorbing over ES and ESM was conducted a good choice for the removal of alizarin.
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- 3.1.1.2. Oxalic acid. Oxalic acid is a useful laboratory chemical, which is
ylene Blue dye from its aqueous solutions. The research group also char- largely used as cleaning or bleaching agent, especially for the removal
acterized ES and ESM chemically and physically and paper includes of rust by easily complexing with iron. It is also used as mordant in dye-
results on these studies. Salman et al. [37] examined the use of ES and ing processes and plays an important role in the metallurgy of lantha-
ESM and their mixture to scavenge three different dyes, Methylene nides. A high concentration of Oxalic acid can be harmful to humans
Blue (cation), Bromophenol Blue (anion) and Methyl Orange (anion) and animals. It is extremely destructive to the tissues of mucous mem-
from their aqueous solutions. It was found that ESM possesses greater branes and upper respiratory tract. On ingestion, it causes congenital
affinity towards Methylene Blue than other two dyes. It was also malformation to the fetus.
ascertained that as compared to ES and the mixture of ES and ESM, Powdered chicken ES of 125 μm sieve size were used to adsorb oxalic
ESM alone possesses higher capacity (about 1.35 to 1.65 fold) to adsorb acid from waste water and kinetics of the process was monitored under
Methylene Blue. The optimum conditions for highest percentage re- batch technique at different temperatures [44]. The adsorbent was char-
moval of Methylene Blue were observed with particle size of 250 μm, acterized through BET surface area, SEM, FTIR and EDS techniques. Pre-
pH 10, at 80 °C, for 30 min with 1.0 g/100 ml adsorbent and 2 mg/ liminary investigations of the ES – Oxalic acid adsorption was
100 ml dye concentration. This approach was further improved by determined with respect to acid concentration and equilibrium time.
Nagadi et al. [38] by varying the operating parameters like contact Freundlich, Langmuir, Tempkin and Harkins-Jura adsorption isotherm
time, pH, dosage of ES powder and temperature. Results obtained indi- models were applied to investigate the ongoing adsorption process.
cated that the best operating conditions for the removal of Methylene Paper also contains results on the intra-particle diffusion, Elovich and
Blue are at pH 10 and temperature 50 °C by using 2 g of ES powder for 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- kinetic study revealed that pseudo second order model fitted well in ki-
sorption process was feasible and spontaneous. netic data, while both the intra particle diffusion and Boyd's kinetic
model indicated that intra particle diffusion was the rate determining
3.1.1.3. Phenol. Phenol is also one of the toxic organic pollutants present step in the ongoing biosorption process. The negative values of both
in the effluents of textile, petrochemicals, pesticides, etc. industries and the enthalpy (ΔH°) and Gibbs free energy (ΔG°) changes indicate exo-
causes serious environment threats to the human beings [45–47]. Its thermic as well as feasible and spontaneous nature of the biosorption
halogen derivatives give a peculiar smell and taste in the water and process.
also pose severe environmental havoc. Because of the toxic nature of
phenol, it has been designated as a priority pollutant worldwide [48]. 3.1.2.2. Removal of pharmaceutics (morphine). Extracted from poppy
In the year 2012, Daraei et al. [49] explored the potential of ES waste straw of the opium poppy, Morphine is a well-known pain reliever.
in the removal of phenol from its aqueous solutions. Batch experiments On administration, it attacks the central nervous system (CNS) and de-
were conducted to evaluate the effect of pH, phenol concentration, dos- creases the feeling of acute pain as well as chronic pain. Morphine is also
age of adsorbent, and contact time on the removal of phenol. In-depth frequently used for relieving pain from myocardial infarction and dur-
kinetic studies of the adsorption process were carried out and ES was ing labour.
also characterized using scanning electron microscopy, Fourier trans- In a recent study, ESM has been used for the extraction of morphine
form infrared spectroscopy, X-ray diffraction, and X-ray fluorescence in biological samples in a solid phase extraction (SPE) format followed
analysis etc. Nearly 0.55 mg/g adsorption capacity was observed at con- by HPLC [55]. The extraction and determination of morphine is very im-
tact time 90 min, 25 °C, pH 9, adsorbent dosage 3.5 g and initial concen- portant for the assessment of analgesics. The chemically modified ESMs
tration of phenol 30 mg/L. The adsorption of phenol over ES was found have been developed by increasing the hydrophobicity through the re-
to be an exothermic and spontaneous process. Boukhlifi et al. [50] fur- action of surface amino groups and glutaraldehyde followed by subse-
ther performed experimental investigations on adsorption and kinetic quent functionalization using different amines. The removal
studies of phenol adsorption and found ES as a potent, natural and performance of ESM was increased from 72 to 88.93% after chemical
eco-friendly adsorbent material for the adsorption of residual phenol modification. The normal hexane amine functionalized ESM with glu-
from effluents. taraldehyde has shown best results in terms of analytical performance
as observed from HPLC chromatograms. These modified amine ESMs
3.1.1.4. Pesticide (malathion). Elwakeel and Yousif [51] investigated ad- are excellent SPE format adsorbents for extraction of morphine from sa-
sorption behavior of Malathion, a commonly used pesticide, on ES and liva samples.
its thermally treated samples, using batch method and also analyzed
the adsorption kinetics as well as adsorption isotherms. The uptake ca- 3.1.2.3. Linear alkyl benzene sulphonates. The intricate lattice network
pacity of ES was found up to 1.928 mmol/g at 25 °C. The adsorption pro- structure of ESM exhibits unique ability to capture linear alkylbenzene
cess followed pseudo first order kinetics and the uptake capacity of egg sulfonates (LAS) by hydrophobic interactions, at pH very close to the
shell was found higher after thermal treatment. isoelectric point of ESM. This phenomenon is similar to the most widely
used trapping mechanism of SPE used for the extraction of LAS. Hence,
3.1.1.5. Humic acid. Humic acid is also one of the main components of ESM has also been evaluated as bioadsorbent in SPE format for the ex-
peat water having a backbone of aromatic and aliphatic residues with traction of LAS [56]. Captivatingly, ESM based adsorbents are found to
numerous substituents such as –OH groups, ketones, carboxylic acid possess low limits of detection, wide linear range, good precision and
groups, amino acids/peptides, saccharides, and amino saccharides. It recoveries under the optimal solid phase extraction conditions. ESM ex-
consists of large molecules with molecular weights ranging from thou- hibits higher extraction recoveries for LAS in the environmental sam-
sands to hundreds of thousands and imparts brown or yellow color in ples. It also shows stronger retention abilities than conventional SPE
peat water. It poses serious environmental problem in drinking water adsorbents, usually alkyl bonded silica and some nanostructured mate-
because of its bad taste and odor [52]. rials, hence can be used to enhance the recovery of LAS. On the basis of
Zulfikar et al. [53] proposed a new approach to remove humic acid HPLC separation and UV detection of LAS homologues, the proposed
from peat water using ES powder. Kinetics of adsorption, influences of system could respond down to 0.027 ng mL−1 of LAS with a linear cal-
pH, contact time, dosage of ES and temperature were studied and ibration range from 0.2 to 100 ng mL−1, showing thereby a good LAS en-
established ES as a highly potential adsorbent for the removal of richment ability of ES membrane biomaterial with high sensitivity, and
humic acid. 5 g of the powdered ES adsorbed nearly 95% of humic acid could be successfully used for the detection of residual LAS in environ-
successfully from the peat water. From Langmuir model, the adsorption mental water samples. ESM is found highly sensitive for the detection
capacity of ES for humic acid uptake was found to be about 126.58 mg/g of LAS and the adsorption capacity was found in the range 30–50 μg/g,
at pH 4.01. The kinetic experimental data proportionally correlated with which is much higher than traditional SPE adsorbents. Furthermore
the pseudo second order kinetic model with a rate constant in the range ESM is economical and easily available and can be modified according
of 0.016–0.112 g·mg−1 min−1, while intra-particle diffusion was the to the need of the experiments.
main rate determining step in the humic acid removal process.
3.1.2.4. Polycyclic aromatic hydrocarbons (PAHs). PAHs are produced
3.1.2. Chemically modified ES & ESM as adsorbents from the incomplete combustion of organic matter. Despite non polar
and lipophilic nature and poor solubility in water, PAHs persist in the
3.1.2.1. Organic dyes. Elkady et al. [54] immobilized ES with a polymer environment. They are carcinogenic and also linked to development of
mixture of alginate and polyvinyl alcohol and developed a biocomposite cardiovascular diseases in humans.
adsorbent (ES composite) for the adsorption of C.I. Remazol Reactive In a recent study, based on ESM templating of LAS, Wang et al. [57]
Red 198 from its aqueous solution. The ES composite thus formed was demonstrated SPE format for the enrichment of PAHs in environmental
characterized using XRD, TGA, FTIR and SEM. The Reactive Red 198 aqueous samples. The effect of various factors, including solution pH,
dye adsorption onto the ES composite was investigated in a batch sys- LAS concentration, ionic strength, and humic acid concentration on
tem with respect to initial dye concentration, pH, contact time, agitation the recoveries of PAHs were investigated and optimized. Authors con-
speed, temperature and adsorbent dosage. The prepared biocomposite cluded that LAS concentration and solution pH had prominent effect
was found to exhibit high efficiency for the dye adsorption and the equi- on extraction of PAHs, while the recoveries of PAHs decreased in the
librium state could be achieved in 3 h. The maximum monolayer dye ad- presence of salt and humic acid. Under the optimized analytical condi-
sorption capacity was estimated to be 46.9 mg/g at 22 °C and pH 1.0. The 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) 376–387 381

with a linear calibration ranging from 0.02 to 10 μg/L; showing thereby a for the sequential injection reductive bio-sorption of Cr(VI) and its spe-
good PAHs enrichment ability with high sensitivity. The developed ciation with detection by electrothermal atomic absorption spectrome-
method was used satisfactorily for the detection of PAHs in environ- try. Cr(VI) was adsorbed onto the surface of ESM with reduction to
mental water samples. Cr(III) ions through transient, unstable species of Cr(V) and Cr(IV),
while Cr(III) was virtually not retained. The experimental procedure in-
3.2. Adsorptive removal of inorganic pollutants cludes the separation and pre concentration of Cr(VI) on ESM at pH 2
and its subsequent detection after elution, followed by conversion of
In the last almost 10 years, utilization of poultry waste in waste Cr(III) to Cr(VI) and then total chromium analysis. Cr(III) concentration
water treatment for removal of toxic metals has attracted much atten- was finally obtained by subtraction. With a sampling volume of 1000 μl,
tion from the researchers all over the world. This section aims to give an enrichment factor of 13.3 was achieved. A linear range of 0.05–
a comprehensive account of utilization of ES and ESM in the removal 1.25 μg/L for Cr (VI), along with a detection limit of 0.01 μg/L and a pre-
of inorganic substances. The removal of toxic metals from waste water cision of 3.2% at the level of 0.5 μg/L, were obtained. Rajendran et al. [64]
is a matter of great interest in the field of water pollution, which is a se- explored the adsorption of Cr(VI) ions onto ES for various influencing
rious cause of water degradation. Numerous metals such as chromium, parameters and arrived at the conclusion that chromium removal
copper, cadmium, lead, mercury, arsenic, manganese, etc., are known to using waste material ES may be an eco-friendly, cost effective, time sav-
be significantly toxic and in recent years their effective removal using ing and more efficient than other conventional technologies to clean up
egg waste materials as adsorbents have been achieved. Moreover, re- chromium contaminated sites. Daraei et al. [65] have worked extensive-
moval and recovery of precious metals like gold, silver, palladium plat- ly on the removal of Cr(VI) from waste water samples using ESM
inum etc. is also an important technological development which could through batch adsorption process. The ESM was characterized using
be easily achieved by ES and ESM adsorbents. SEM, FTIR, and XRF analysis and its feasibility for adsorption of Cr(VI)
was evaluated. The experimentally gathered data was compared with
3.2.1. Natural ES & ESM as adsorbents theoretical calculations based on central composite design (CCD) with
the variable parameters. The optimum conditions for maximum remov-
3.2.1.1. Actinides. Both Uranium and Thorium are important elements of al of Cr(VI) were derived using CCD so that ESM can be utilized for max-
actinide series. They are naturally occurring, radioactive substances. As imum removal of metal ions. Based on the results of the CCD, the
far as their toxicity is concerned it is well documented in literature. On maximum removal (81.47%) was achieved at temperature 20 °C,
breathing air containing uranium, its particles can easily enter into kid- pH 3.54, Cr(VI) ion concentration 5.0 mg/L, time 117.52 min, and dosage
neys through bloodstream and can damage kidney cells. A high uranium 3.78 g. In another report Daraei et al. [66] established that the adsorp-
intake can cause acute kidney failure and death. Both U & Th are alpha tion of Cr(VI) ions onto ES occurs through ion exchange mechanism car-
emitter and their isotopes pose severe radiation hazards towards bonate groups present on adsorbents play significant role, due to its
humans by developing cancer. cation exchange properties. Authors also characterized ES and opti-
The first and the only report on the use of egg waste material as ad- mized the parameters such as, pH, Cr(VI) ions concentration, amount
sorbent for the removal of an inorganic material appeared in 1999 in of ES, contact time, temperature for Cr(VI) removal from aqueous solu-
which ESM was used for the removal of actinides from dilute waste ac- tions. The extraction efficiency of ES for the removal of Cr(VI) ions was
tinide solution [58]. The adsorption of radioactive elements Uranium found higher than Cr(III) ions and approximately 93% of Cr(VI) ions
and Thorium was investigated and time dependency, pH profile, ad- were removed at 25 °C at pH 5 in 90 min. Thermodynamic parameters
sorption capacity were experimentally measured. ESM accumulated like, change in enthalpy (ΔH0), change in entropy (ΔS0), and change
uranium to a larger extent than thorium even from dilute aqueous solu- in free energy (ΔG0) were calculated for the ongoing adsorption pro-
tions through pH adjustment. ESM was found very effective for remov- cess. Chromium adsorption kinetics was also found to be fitted in pseu-
ing actinides from aqueous solutions and 60 and 240 mg adsorption of do-first-order kinetic model. Quite recently, Kumaraswamy et al. [67]
Th(VI) and U(VI) respectively were achieved by 1 g of ES. The developed improved this approach for the large scale application of ES for the re-
method was proposed to be used in filtration technology. moval of Cr(VI) from waste water under industrial conditions. The de-
tailed performance analysis was carried out as function of various
3.2.1.2. Chromium. Chromium is widely used in industrial applications operating parameters such as contact time, initial concentration, adsor-
such as electroplating, cement, steel, dyes, aluminum, leather tanning, bent dose, and particle size. The parameters affecting kinetics and equi-
metal finishing etc. and unregulated disposal of effluents containing librium of Cr(VI) adsorption onto ES powder were also determined very
chromium has led to contamination of soil and ground waters [59]. precisely.
Though metallic chromium is not toxic but ionic forms of chromium,
which are present in industrial effluents, possess potential hazardous 3.2.1.3. Copper. Copper is another toxic metal which poses potential
effects on human health as well as animals. It is now well established threat to the human health and environment, even at low concentra-
that hexavalent chromium Cr(VI) is much more toxic than trivalent tions. Its toxicity is also called copperiedus, which is mainly due to ex-
chromium Cr(III) [60]. Cr(VI) is carcinogenic and mutagenic to the living cess of copper in the human body. Copperiedus can occur by eating
organisms, and also considered much more hazardous than any other acidic foods cooked in uncoated copper cookwares or through exposure
heavy metal. According to environment protection agencies, the thresh- to excess copper in drinking water or any other environmental resource.
old contaminant level of total chromium in public water systems is It is also pertinent to note that copper present in organic form, like that
100 ppb [61]. found in food, possesses beneficial micronutrient nature, while inorgan-
In the year 2005, Chojnacka [62] studied the biosorption of Cr(III) ic metallic copper is a toxic heavy metal and its toxicity symptoms are at
from its aqueous solutions by ES and studied effect of various parame- par with mercury and lead. The accumulation of copper in human body
ters on the adsorption process. Crushed ES was found to possess almost causes skin, brain, pancreas and heart diseases [68]. The permissible
double adsorption capacity (21–160 mg/g) than activated carbon and limit of copper is 2.5 mg/L in water. Wastewater from various industries,
animal bones. The maximum experimentally determined adsorption such as plastic, metal finishing, electroplating, pigments, and mining
capacity 160 mg/g was obtained at low adsorbent concentration, 20 °C contains copper.
and pH 5. ES was able to remove Cr(III) ions to a level lower than per- Carvalho et al. [69] performed a comparative study to evaluate the
mitted by environmental regulations, at a temperature of 40 °C, adsor- adsorption efficacy of ES in treatment of simulated effluents and real in-
bent concentration of 15 g/L and initial concentration of metal ions dustrial effluents to assess the adsorption capacity of ES powder in re-
100 mg/kg. Zou et al. [63] further improved this approach using ESM 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 commonly referred as “Lead poisoning” and severely affects central ner-
anodizing plant. Results indicated that ES can remove several pollutants vous system of the human being, causing behavior disorders. Other
from different types of aqueous systems, with great efficiency. The ES common symptoms of lead poisoning are confusion, headache, abdom-
adsorbent was found to possess better affinity for copper than for chlo- inal pain, anemia, irritability and coma. Presence of lead in waste water
ride and additionally, the results obtained for the adsorption of alumi- is well documented and a variety of approaches have been presented in
num proved that ES works as an effective adsorbent in wastewater literature for the removal of lead from aqueous solutions.
from anodizing plants. Authors reported that the use of ES in real A research was conducted to optimize the removal of lead from bat-
waste water effluents does not require any change in operating condi- tery manufacturing waste water using hen ES and duck ES [74]. Natural
tions of the adsorption procedures to apply this technique to real treat- hen and duck ES have more protein fiber than boiled hen and duck ES,
ment conditions. 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
3.2.1.4. Cadmium. Cadmium is a highly toxic metal with very low per- percentage removal of lead ions. As the main component of ES is calci-
missible exposure limit. It is widely used in electroplating industries um carbonate, its hydrolysis gives basic solution and the pH of the solu-
and in the manufacturing of cadmium containing batteries. Several in- tion is further increased on increasing the amount of the adsorbent. The
dustrial paints also contain Cadmium. “Cadmium Blues” is the common optimum pH for lead removal was found 6. This study also concluded
name for the acute chromium exposure, which leads to flu-like symp- that lead removal involved more than one type of mechanism i.e. ad-
toms including fever, cough, dryness, irritation of the nose and throat sorption and precipitation. At higher dosage of ES, the final pH was N4
and muscle pain. A long exposure to cadmium may lead to respiratory and solubility of lead decreased and consequently precipitation of lead
problems, damage to the liver and renal failure. It is also a well known occurred as lead hydroxide complex. The final concentration of lead
carcinogen. was found lower than the waste water quality standards. Nearly
Characteristics of Cd ion removal by adsorption over ES have been 78.03% lead was removed at pH 6, contact time 90 min and 1.0 g of ad-
investigated for various parameters and adsorption was found to in- sorbent in 100 ml of battery manufacturing waste water. In a recent re-
crease with the increase in reaction time, the amount of ES, temperature port [75], a biosorbent derived from co-composting ES (30% w/w)
and pH. However, the amount of adsorption decreased with the in- mixed with organic materials like potato peels, grass clipping, and rice
crease in the ES size. The paper also includes verification of various ad- husk) was used for the adsorption of Pb(II) from its aqueous solutions.
sorption isotherms and reaction kinetics [70]. Recently, Cano et al. [71] The performance of the compost ES was also compared with matured
researched extensively to investigate the mechanism and capacity of compost without ES and natural ES and about 43% increase in its sorp-
adsorption of cadmium ions onto chicken ES. The ES was also character- tion capacity was observed. Sorption kinetics and equilibrium data
ized through XRD. The point of zero charge (PZC) of the ES was found to were found fitted to pseudo-second-order and Langmuir models,
be 11.4. The adsorption capacity of ES increased while raising the pH respectively.
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 3.2.1.6. Precious metals. Precious metals have wide range of applications
of Cd(II) occurred mainly onto the calcareous layer of the ES, but slightly in various industries, agriculture and medicine, because of their specific
on the membrane layer. Authors reported that the adsorption of Cd(II) physical and chemical properties. These metals are very rare, mostly
was not reversible, and the main adsorption mechanisms were precipi- occur in their elemental form and possess high economic values. Gold
tation and ion exchange. On the average, the contributions of the nonre- (Au), Silver (Ag), Platinum (Pt) and Palladium (Pd) are internationally
versible and reversible mechanisms were 68% and 32%, respectively. An recognized forms of currency under ISO 4217.
important finding was that Cd(II) precipitated as (Cd/Ca)CO3 on the sur- Ishikawa et al. in the year 2002 [76], evaluated ESM for the uptake
face of the ES during the adsorption of Cd(II). In a recent report [72], ad- and recovery of gold ions from its solutions and electroplating waste
sorption of Cd was carried out over well grinded ES and maximum water. The ESM used was dried, grounded and sieved into various
monolayer adsorption capacity of 329 mg/g was achieved. Presence of sizes. Gold dicyanoaurate (I) and tetrachloroaurate (III) ions have
aragonite phase obtained due to phase transformation from calcite dur- been adsorbed from waste water and recovered through desorption
ing milling was considered the basic reason for such a high adsorption. with sodium hydroxide solutions. The adsorption capacities for Au(I)
Adsorption was found to be obeyed through by Langmuir, Freundlich and Au(III) over ESM were found as 147 and 618 mg/g, respectively. Se-
and Dubinin–Radushkevich isotherms and second order rate kinetics lective recovery of gold ions in presence of other ions was also investi-
through intraparticle diffusion process. Another work by Aldaco et al. gated in a flow through sorption column system and gold was found
[73] demonstrated utilization of ES as a source of calcium to improve to possess highest affinity for metal sorption among other metal ions.
the adsorption capacities of commercial carbons to adsorb cadmium The experimental findings suggested potential applications of ESM
from water along with nickel and zinc. The maximum adsorption capac- biosorption column systems in recovery and refining of gold.
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 3.2.1.7. Light metals. Pettinato et al. [77] attempted to remove water pol-
adsorbents without modification. The improvement of adsorbent per- luting metal ions Al3+, Fe2+ and Zn2+ by powdered ES and ESM and ap-
formance was related to the formation of calcium phosphate on the car- plied these as potential adsorbents to improve membrane biological
bon surface and adsorption studies in binary metal solutions were also reactor (MBR) based technology used in sewage treatment process.
performed to identify the competitive effects in multicomponent ad- The development of technology was based on two steps. In the first
sorption, using calcium-modified carbons. The adsorption of Cd2 +, step concentration and size effect of the ES and ESM on fouling was con-
Zn2+ and Ni2+ ions was also affected by the co-ion competition, espe- ducted to establish compatibility between the two processes. While, in
cially at high metal concentrations and the metal uptake reduction the second step quantitative analysis was made to evaluate adsorption
ranged from 0.1 to 77%. capacities of both the adsorbents by passing aqueous solution contain-
ing mixtures of Al3+, Fe2+ and Zn2+ through the reactor. Quite encour-
3.2.1.5. Lead. Another metal present in industrial effluents is lead, which aging results have been found and it was concluded that application of
is highly toxic and detrimental to environment because of its non biode- ES and ESM in MBR technology is a better option.
gradable and persistent nature. It is widely used in petrol refining,
sulphuric acid manufacturing, manufacture of pigments, ceramics and 3.2.1.8. Fluorides. Fluoride is another toxic inorganic pollutant present in
plastics, storage batteries etc., hence found in waste water arising nature, which pose significant health hazards to humans. A fluoride
from these processes. The presence of lead in the human body is containing drinking water is highly endemic and its excessive intake
A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387 383

leads to the loss of calcium from the tooth matrix resulting thereby in- process, hence PEI–ESM bioadsorbent could detoxify Cr(VI) through
curable aggravating cavity formation for entire life period [78]. Accord- its reduction to less toxic Cr(III) ions. In a most recent publication,
ing to the WHO recommendations maximum permissible limit for Chen et al. [84] used chemically modified ES biosorbent to remove phos-
fluoride in drinking water is 1.5 mg/L [79]. phate and Cr(VI). The chemical modification of ES surface was made by
Bhaumik et al. [80] in the year 2012 explored the potential of ES using α-FeOOH (F-ES) and ascertained through EDS, XRD and FTIR anal-
powder as an adsorbent for the removal of fluoride from aqueous solu- yses. It was also observed that by increasing the sorption sites through
tions and conducted equilibrium, kinetic and thermodynamic studies. modification adsorption of phosphate and Cr(VI) could be enhanced.
Fluoride adsorption was studied in a batch system where adsorption The unmodified ES adsorbed 89.74 and 11.81 mg/g phosphate and
was found to be pH dependent with maximum removal efficiency at Cr(VI), while F-ES increased it to 248.73 and 41.57 mg/g, respectively.
6.0 and energy of activation was found to be 45.98 kJ/mol by using Ar- Kinetics of the adsorption was also monitored and the kinetics data
rhenius equation, indicating chemisorption nature of fluoride onto ES were found fit with pseudo-first and second order kinetics equations.
powder. Authors concluded that adsorption of fluoride ions onto ES Richie kinetics model was also applied and it was found that the adsorp-
powder is spontaneous and exothermic and ES powder can be used as tion on ES was controlled by multiple mechanisms.
an effective, low cost adsorbent for fluoride removal from aqueous solu-
tions as well as ground water. In another study, an alumina supported 3.2.2.2. Copper. In the year 2010, Ahmad et al. [85] developed an iron
carbon composite material with exceptionally high defluoridation prop- oxide coated ES powder for effective removal of Cu ions from aqueous
erty was developed from ES [81]. ES waste was used as calcium source solutions. The adsorption characteristics of iron oxide coated ES powder
for the synthesis of ES composite that can be used as an adsorbent for (IOESP) were systematically studied in batch as a function of contact
selective fluoride adsorption from aqueous solutions. The effect of vari- time, pH, metal ion concentration, and temperature. The IOESP was pre-
ous synthesis parameters like ES – ESM ratio, aluminum loading, mixing pared by chemical precipitation of FeSO4·7H2O onto hen ES powder. It
time and calcinations temperature were optimized. ES composite was exhibited a remarkably enhanced adsorption capacity for Cu2 + than
also characterized for elemental composition, morphology, functionali- the pure iron oxide and ES powder. The equilibrium data fitted well to
ty and textural properties. The adsorption capacity of ES composite was Freundlich isotherm, which suggested heterogeneity in the adsorption
37 mg/g at 303 K and it could be used over a wide range of pH 3–9. This sites. Regeneration of metal ion were performed using HCl, EDTA,
composite was more selective and efficient for fluoride removal and HCOOH and NaOH as eluting agent from saturated IOESP and the max-
proved to be a potential, indigenous and economic adsorbent for fluo- imum regeneration was observed with HCl. The adsorption of Cu2+ was
ride removal. found to increase in the presence of anionic surfactant, while cationic
surfactant showed no significant change in adsorption capacities. Ther-
3.2.2. Chemically modified ES & ESM as adsorbents modynamic parameters indicated that the adsorption of Cu2 + onto
IOESP was feasible, spontaneous, and exothermic. The maximum mono-
3.2.2.1. Chromium. In recent years, selective and enhanced metal ion ad- layer adsorption capacity of this modified ES powder for Cu2+ removal
sorption from waste water solutions was achieved by modified adsor- was found 44.843 mg/g.
bents. Guo et al. [82] prepared novel inorganic biocomposite Mg/Al-

CO2–3 and Mg/Al-Cl layered double hydroxide (LDH)/ESM membrane. 3.2.2.3. Arsenic. Arsenic is another highly toxic pollutant present in in-
In this biocomposite, ESM served as a substrate and template to immo- dustrial effluents related to pesticides production, wood preservatives,
bilize the LDH, formed by an in-situ hydrothermal crystallization meth- glassware production, electronics industries etc. [86,87]. The inorganic
od. These biocomposites were then used as adsorbents for the removal form of Arsenic is considered more toxic than organic form i.e.
of Cr(VI) ions. The removal efficiency of ESM for removal of Cr (VI) ion aresenites present in drinking water in the trivalent form are more
was increased from 80 to 90% at pH 4. ESM served as adsorbent as toxic than organic arsenates of pentavalent form [88]. Arsenic have
well as support to uniformly disperse LDH and hence its adsorption per- caused a potential threat to human health owing to its carcinogenic ef-
formance increased significantly. The composite membranes removed fects on lungs, kidneys, liver, bladder, hematopoietic system, and the
Cr(VI) ion more efficiently than physical mixtures of LDH and ESM. central nervous system, cardiovascular diseases, and dermal changes
Higher percentage of Cr(VI) ion was extracted at pH 5 using ES powder, [89]. A long exposure to arsenic may cause deficiency of vitamin A caus-
however the pH values reported for highest extraction were 2.0 and 5.1 ing thereby heart diseases and night blindness.
for ESM and CO2– 3 loaded LDH–ESM, respectively. The adsorption ability Considering the potential toxicity of arsenic, Zhang et al. [90] con-
of LDH in composite membrane was further enhanced by the develop- ducted a study to utilize ESM as SPE adsorbent for the retention of arse-
ment of Cl− LDH/ESM composite membrane through an anion ex- nic in combination with hydride generation atomic fluorescence
change treatment method well characterized through SEM and XRD spectrometry (HG-AFS). It was reported that under the optimal condi-
patterns. The method was found highly effective for extracting metal tions, As(V) could be easily extracted by the ESM packed cartridge and
at natural pH of the solution. The maximum percentage removal of the breakthrough adsorption capacity was found to be 3.9 μg/g. The fa-
Cr(VI) was at pH 4 and at a temperature of 20 °C because at greater vorable limit of detection for As(V) was found to be 0.001 μg/L with an
pH the fat from the adsorbent is dissolved to the water, which resulted enrichment factor of 33.3, and the relative standard deviation was 2.1%
into the turbidity, leading thereby poor adsorption of Cr(VI) ions on the for 0.6 μg/L of As. The proposed method was also successfully applied for
ESM surface. In an advanced research, Liu and Huang [83] developed a the analysis of As(V) in aqueous environmental samples. In another
novel bioadsorbent for adsorption and detoxification of Cr(VI) from study, Chen et al. [91] demonstrated the most interesting approach for
water. The polyethyleneimine (PEI) functionalized biosorbent using an the development of green biosorbent through modification of the sur-
ESM as a model was synthesized, based on the cross linking reaction be- face of ESM focusing on certain functional groups for ultra-high selec-
tween aldehydes in glutaraldehyde, and the functional groups such as tive uptake of As(V) against As(III) with detection by hydride
amides and amines present in ESM. The prepared biosorbent interacted generation atomic fluorescence spectrometry. The presence of carbox-
strongly with Cr(VI) and the dynamic uptake capacity of the PEI–ESM ylic groups on ESM surface restricted the arsenic adsorption, hence,
increased by nearly 105%. The maximum equilibrium adsorption capac- ESM was modified by esterification with methanol and the methyl es-
ity for Cr(VI) was found to be about 160 mg/g with an initial pH of 3.0 terified ESM (MESM) was explored for adsorption of Arsenic from
after this modification. Raman spectroscopy and X-ray photoelectron waste water samples. As a novel green adsorbent material, MESM ex-
spectroscopic analysis, performed on the prepared biosorbent before hibited 200 fold improvements on adsorption capacity of arsenate
and after Cr(VI) adsorption suggested that some of adsorbed Cr(VI) an- with respect to bare ESM. It presented an ultra-high selectivity of
ions were reduced to Cr(III) in Cr2O3 or Cr(OH)3 during the sorption 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- 3.3. Applications of ESM nanoparticles
sorption of As(III) was observed. This provided great potential for selec-
tive uptake of arsenate in the presence of arsenite. Thus total inorganic In the last 2–3 years some of the adsorption abilities of particularly
arsenic could be removed by converting As(III) to As(V) and following ESM nanoparticles have been explored to derive certain typical and use-
the same adsorption process. The results were confirmed by graphite ful applications.
furnace atomic absorption spectrometry and spiking recovery. Authors One of the researches includes the use of ESM nanoparticles in Lith-
concluded that MESM provided a practical approach for the speciation ium – Sulphur cell to improve its efficiency. Chung, and Manthiram [96]
of inorganic arsenic species in real waste water samples. 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
3.2.2.4. Mercury. Mercury is one of the most toxic heavy metals, which is
improved performance, efficiency and long-term cyclability to Li\\S
dangerous to humans in elemental as well as ionic forms. The elemental
battery. Thus polysulfide absorbent for highly stable and reversible
form of mercury can exists in vapor and liquid states and exposure of
Li\\S Cells were developed from a natural ESM. In another research
both the states is fatal for the humans and can cause blocking of blood
published in the year 2015, protein cavities present in ESM were used
vessels. Other toxic effects of the metal include damage to the brain, kid-
as natural biotemplate for the growth of nanoparticles [97]. Fibrous
neys and lungs. Sensory impairment, disturbed sensation and lack of co-
oxide ceramics were prepared by wet impregnation of biological tem-
ordination are common symptoms of mercury poisoning.
plate with water solution of cerium nitrate. Unique bio-morphic CeO2
Cheng et al. [92] in the year 2010 developed a thiol functionalized
microstructures with interwoven networks were synthesized and char-
ESM through esterification between thioglycolic acid and oxygen-con-
acterized by scanning electron microscope (SEM) and X-ray diffraction
taining functional groups. The potential biosorbent thus formed was
(XRD), whereas low-temperature nitrogen adsorption (BET) method
used for the removal of toxic mercury in wastewater solutions. The
was used in order to characterize porous properties. Pramanik et al.
modified ESM greatly enhanced the adsorption capacity for Hg2+ and
[98] introduced water soluble blue-emitting Au\\Ag alloy nanoparticles
the maximum capacity was increased N 3-fold in comparison with the
and fluorescent solid platforms for the removal of dyes from water by an
unmodified ESM, from 19.4 mg/g to 71.9 mg/g. This novel thiol-func-
ESM-induced reduction process. Chicken ESM, was used to prepare
tionalized ESM was able to remove and recover mercury even from
nano clusters of gold (Au), silver (Ag) and their bimetallic (Au\\Ag)
very low concentration of mercury from wastewaters. This approach
alloy at room temperature, without using any reducing agent or cata-
was further improved in the year 2013 by Wang et al. [93], who studied
lyst. The Au and Au\\Ag alloy clusters were highly fluorescent and ex-
adsorption of mercury along with several other toxic heavy metal ions
hibited intense blue emission around 435 ± 5 and 440 ± 5 nm,
from aqueous solutions on ESM functionalized with ammonium
respectively. These metal clusters immobilized inexpensive ESMs have
thioglycolate. Thiol functionalization was based on the reduction of di-
also been explored in removing organic dyes from water. Authors re-
sulfide bonds in ESM by ammonium thioglycolate. Authors character-
ported that ESM can be converted into an effective platform for water
ized thiol-functionalized ESM and investigated its application as an
purification because of its strong adsorption of the dye molecules in
adsorbent for the removal of Hg(II), Cr(VI), Cu(II), Pb(II), Cd(II), and
the presence of the metal particles. This process has the dual advantages
Ag(I) from waste water samples. The experimental results revealed
of utilizing an inexpensive, abundant and eco-friendly food waste for in
that the adsorption abilities of the thiol-functionalized ESM towards
situ reduction and formation of metal nanoparticles and the utilization
Hg(II), Cr(VI), Cu(II), Pb(II), Cd(II), and Ag(I) improved 5.5, 1.6, 7.7,
of the same as an effective platform for the removal of anionic dyes
12.4, 12.7, and 21.1 fold, respectively, compared with that of the ESM.
from waste water.
The developed membrane was used as column packing material to fab-
ricate column for wastewater purification.
3.4. Carbonate hydroxylapatite as adsorbent

3.2.2.5. Gold. In another novel development, Shoji et al. [94] proposed a Carbonate hydroxylapatite (CHAP) is a nanostructured material,
bead type adsorbent made from chitosan and ESM with improved ad- which is synthesized by using ES waste as a raw material. CHAP is con-
sorption efficiency for precious metal ions. The ESM-conjugated chito- sidered as expensive material because of the use of high purity reagents
san beads were examined for recovery of gold ions from dilute in its synthesis [99]. It is indeed a calcium phosphate ceramic material,
aqueous solutions as well as selective adsorption from mixtures of which possesses extensive biomedical applications. It is also used as po-
metal ions. Based on the experimental findings, ESM conjugated chito- tential adsorbent and recently has been utilized for the removal of lead
san beads adsorbed gold and copper up to 100% and 2% respectively and cadmium ions from waste water. Synthetic carbonate HAP (CHAP)
from mixture of gold and copper ions. Authors presented a new prom- has higher efficiency in the removal of heavy metals, but their adsorp-
ising modified adsorbent for the selective uptake of gold ions. In the tion characteristics were not investigated probably due to their high
year 2007, Goto [95] widely researched protein rich biomass, a cost of preparation [100,101].
byproduct in the food and agricultural industries, for the selective re- Lead ions have a relatively high affinity for CHAPs. Liao et al. [102] in-
covery of precious metal ions from industrial waste water without vestigated the kinetics of removal of lead ions by CHAP derived from ES
extra emissions of carbon dioxide. Mechanistic aspects of the metal waste. The effect of lead concentration, contact time, pH was observed
ions adsorption onto protein rich biomass were taken into account in batch experiments. The adsorption of lead ions onto CHAP involved
and selective recovery of the targeted metal ions due to their specific in- two types of interactions, one ion exchange between lead and calcium
teraction with the functional groups present in protein structures was ions and another complexation of lead ions by CHAP. Increase in pH of
also demonstrated. A comparative study was conducted between puri- the solution decreased the net positive charge on CHAP and hence fa-
fied proteins and ESM (90% protein) for the uptake of gold and platinum vored complexation mechanism. The adsorption procedure favored
ions and the adsorption selectivity of protein rich biomass was found pseudo second order kinetic model having higher value of regression
very similar to that of purified proteins. The precious metal ions bound- coefficient (R2 = 0.9991) and Langmuir adsorption model with regres-
ed to the proteins were recovered by nitro hydrochloric acid after char- sion coefficient value of 0.9995 as compared to 0.8002 of Freundlich
ring the metal bound biomass. Au3 + and Pd2 + were successfully model. Maximum lead ion concentration that could be adsorbed onto
recovered from a metal refining solution and a metal plating waste CHAP derived from ES is 101 mg/g, which is far greater than ES adsorp-
using the biomass. An environmental friendly recycling system was pro- tion capacity for lead ions, however the calculated monolayer adsorp-
posed for precious metal ions using protein-rich biomass with an ex- tion capacity was 94.3 mg/g at pH 6 with metal ion concentration of
tremely high loading potential 250 g/kg for gold ions. 10–500 mg/L. This work has established CHAP extracted from ES
A. Mittal et al. / Journal of Molecular Liquids 223 (2016) 376–387 385

waste as efficient adsorbent for lead removal. On comparing the results radioactive substances, lanthanides, etc. Captivatingly, in last two
of previous workers [103–106], CHAP possessed higher extraction effi- years, uses of ESM nanoparticle adsorbent in fuel cell, bio-templates
ciency than calcium HAP (85 mg/g), activated carbon (31.20 mg/g) and water purifier have elevated the importance of ES and ESM. Though
and wheat bran (87 mg/g). In another development, CHAP derived use of CHAP obtained from egg shell waste is not very cost effective but
from ES waste was characterized for physical and chemical properties the removal of Pb and Cd ions using nanostructured CHAP is highly
minimizing contaminants for its potential use in lead removal [107]. efficient.
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-
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