Influencia de La Molienda Sobre Adsorción de Los Residuos de Cáscara de Huevo

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Inuence of milling on the adsorption ability of eggshell waste

Matej Balaz*, Jana Ficeriova, Jaroslav Briancin

Department of Mechanochemistry, Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, 04001 Kosice, Slovakia

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

Eggshell waste is an effective adsor-

bent of heavy metals.

The selectivity of the ESM towarddifferent ions was conrmed.

The effect of milling on the adsorp-

tion ability is different for ES and

ESM.

Two-fold morphology of the milled

ES was observed.

ES is suitable for the adsorption of

Ag(I) from the industrial waste.

a r t i c l e i n f o

Article history:

Received 11 October 2015Received in revised form

24 November 2015

Accepted 1 December 2015

Available online 30 December 2015

Handling Editor: Xiangru Zhang

Keywords:

Eggshell

Eggshell membrane

Adsorption

Silver

Cadmium

Milling

a b s t r a c t

Eggshell waste was successfully used for the removal of heavy metal ions from model solutions. The

effect of ball milling on the structure and adsorption ability of eggshell (ES) and its membrane (ESM) wasinvestigated, with the conclusion that milling is benetial only for the ES. The adsorption experiments

showed that the ESM is a selective adsorbent, as the adsorption ability toward different ions decreased in

the following order: Ag(I) > Cd(II) > Zn(II). The obtainedQmvalues for Ag(I) adsorption on the ESM and

ES were 52.9 and 55.7 mg g1, respectively. The potential industrial application of ES was also demon-

strated by successful removal of Ag(I) from the technological waste.

2015 Elsevier Ltd. All rights reserved.

1. Introduction

The pollution of the environment is an actual issue with high

priority these days. Among its various types, the contamination of

water by heavy metal ions as a result of the industrial processes

taking place in the vast number of plants signicantly contributes

to the to the overall pollution of the environment. Therefore, the

purication of these wastewaters is of high priority (Barakat, 2011;

Fu and Wang, 2011). Heavy metal ions are numerous, however for

this study, three particular were selected (namely cadmium(II),

silver(I) and zinc(II)). Cadmium(II) is one of the most dangerous

ones, as it represents a signicant hazard for human health (Godt

et al., 2006; Bernhoft, 2013). Silver is a noble metal, which has

been widely employed in the photographic and imaging industry

for many years. The accumulation of silver(I) ions in organisms

(including humans) through the food chain causes numerous* Corresponding author.E-mail address:[email protected](M. Balaz).

Contents lists available at ScienceDirect

Chemosphere

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m/ l o c a t e / c h e m o s ph e r e

http://dx.doi.org/10.1016/j.chemosphere.2015.12.002

0045-6535/

2015 Elsevier Ltd. All rights reserved.

Chemosphere 146 (2016) 458e471
mailto:[email protected]://www.sciencedirect.com/science/journal/00456535http://www.elsevier.com/locate/chemospherehttp://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://dx.doi.org/10.1016/j.chemosphere.2015.12.002http://www.elsevier.com/locate/chemospherehttp://www.sciencedirect.com/science/journal/00456535http://crossmark.crossref.org/dialog/?doi=10.1016/j.chemosphere.2015.12.002&domain=pdfmailto:[email protected]


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diseases and disorders (Schmahl and Steinhoff, 1960; Rosenmanet al., 1979, 1987). Zinc(II) is the least dangerous from the selected

ions, as it is a major micronutrient in the human body (Hambidge

and Krebs, 2007). However, too much zinc(II) in the human body

can also cause serious problems like stomach cramps, anemia,

damage to the pancreas, etc. (Naito et al., 2010). Different methods

have been used for the effective removal of all these ions from

wastewater, among which the adsorption by biosorbents has an

inevitable place (Veglio and Beolchini, 1997; Mack et al., 2007;

Demirbas, 2008). Moreover, it was shown recently that after the

removal of Ag(I) by a biocompatible material, the Ag-laden sorbent

exhibits an antibacterial activity (Yao et al., 2013).

The eggshell is one of the most common biomaterials in nature.

It serves its important role in the development and production of

eggs (Hinckeet al., 2011), however afterthe breakage of the egg andremoval of the inner content used further, the eggshell waste is

very often simply discarded and disposed at landlls. The eggshell

wastecomprises the eggshell (ES) itself and the eggshell membrane

(ESM). It represents 11% of the total weight of the egg. The main

component of the ES is calcite CaCO3 (94%). Other components

include MgCO3 (1%), Ca3(PO4)2 (1%) and organic matter (4%)

(Stadelman, 2000).The ESM isa brous proteinous structure which

serves its unique purpose within the egg (Nys et al., 2004). Despite

being treated as a waste, both components have multidisciplinary

applications. The ES can be used, e.g. as a source of calcium for the

synthesis of hydroxyapatite (Gergely et al., 2010), as a precursor for

composite materials (Ghani and Young, 2010) or as a source of

calcium oxide forthe sorption of CO2 (Mohammadi et al., 2014). The

ESM is suitable for a wide spectrum of applications too which wererecently reviewed inBalaz(2014). Namely its use as a biotemplate

(Suet al.,2008) or biosensor (Liet al., 2008) can be mentioned. Both

discussed biomaterials can be also utilized as a biosorbent of heavy

metal ions (Suyama et al., 1994; Park et al., 2007; Shimada et al.,

2010; Ahmad et al., 2012; Daraei et al., 2013; Flores-Cano et al.,

2013; Shaheen et al., 2013). The ESM was reported to exhibit a

signicant selectivity toward different heavy metal ions, due to

which it could be used as a stationary phase in a column chroma-

tography (Ishikawa et al., 2002). The adsorption of cadmium(II)

(Kuh and Kim, 2000; Koumanova et al., 2002; Cheng et al., 2011a;

Flores-Cano et al., 2013) and silver(I) (Cheng et al., 2011b; Ho

et al., 2014) on both discussed biomaterials is of particular inter-

est. The adsorption of zinc(II) of the ES was studied extensively (de

Paula et al., 2008; Shaheen et al., 2013), however the successful

adsorption of zinc(II) on the ESM was not reported until now.

The adsorption ability of the bio-sorbents can be increased by

their modication (Orolinova et al., 2010; Leyva-Ramos et al., 2012;

Wang et al., 2013; Suresh et al., 2014). Milling is one of the effective

methods (Balaz, 2000; Bujnakovaet al., 2013). It can be generally

said that the inuence of milling on cation-exchange properties of

sorbents is practically unexplored, with exception of few papers

(Montinaro et al., 2007; Janusz et al., 2010; Balaz et al., 2015a).

Depending on the intensity of milling, it is possible to only slightly

activate the sample, or to perform reactions which need a large

quantum of energy supply in order to proceed (Balaz, 2008; Balaz

et al., 2013b). The potential of milling to increase the adsorption

ability of the eggshell was reported very recently (Balaz et al.,

2015a), however the effect of milling on the ESM was not investi-

gated until now.

The aim of this study was to investigate the effect of milling of

the eggshell waste biomaterials on their adsorption ability toward

silver(I) ions. Although quite similar study was published recently

(Ho et al., 2014), the novelty in this paper lies in the introduction of

milling procedure and analyzing the results in more detail by

applying Langmuir and Freundlich models to describe the adsorp-

tion process. The real application of the ES to remove silver(I) from

the technological waste and the impact of mild milling on thephysico-chemical properties of the ESM were also investigated.

Moreover, the ESM was used also for the adsorption of cadmium(II)

and zinc(II) ions to conrm its selectivity. Finally, the desorption

behavior of the metal-laden ESM is reported and the adsorption

ability of the two studied materials is compared in detail. The main

idea of this paper is to show that the eggshell waste represents an

interesting selective material for the potential removal of heavy

metal ions from wastewaters and should not just be discarded.

2. Materials and methods

2.1. Materials

Raw eggshell containing the eggshell membrane was providedbya selected canteen in Kosice. The pure ES and ESMwere collected

by the same procedures, as were described in our previous works

((Balazet al., 2013a) and (Balazet al., 2015a), respectively). Cad-

mium nitrate tetrahydrate Cd(NO3)2.4H2O (ITES, Slovakia), silver

nitrate AgNO3 (Merck Millipore, Germany), zinc nitrate hexahy-

drate Zn(NO3)2.6H2O (Sigma-Aldrich, United Kingdom), sodium

hydroxide NaOH (ITES, Slovakia) and nitric acid HNO3 (ITES,

Slovakia) were used as chemicals without further purication. The

technological waste containing silver(I) ions was obtained from the

company DOMA, a.s., Presov and its chemical composition was

analyzed by atomic absorption spectroscopy.

2.2. Milling

The milling of both biomaterials was peformed in a laboratory

planetary ball mill Pulverisette 6 (Fritsch, Germany) under slightly

different conditions. The common conditions comprised the

following: loading of the mill- 50 balls of 10 mm diameter; ball

chargein the mill-360 g; material of the milling chamber and balls-

tungsten carbide; atmosphere-air; laboratory temperature.

The differences were in rotation speed of the planet carrier (i.e.

milling speed), sample mass, milling time and ball-to powder ratio

(BPR). These conditions are listed inTable 1.

In order to clearly label the different ES/ESM samples discussed

within the paper, the numbers describing the duration of milling

are given immediately after the abbreviation ESor ESM, e.g. the

abbreviation ESM0 corresponds to the non-milled ESM, ES360

stands for the ES milled for 360 min, etc.

List of symbols

BPR ball-to-powder ratio

b constant of the Langmuir isotherm related to the

heat of adsorption (L.mg1)

ce equilibrium solution concentration of ions (mol.L1)

cs amount of the adsorbed ions (mol.g1

)E free energy of adsorption

ES eggshell

ESM eggshell membrane

Kf Freundlich constant

nf constant representing the adsorption intensity of

the adsorbentqe-amount of ions adsorbed at

equilibrium (mg.g1)

Qm maximum monolayer adsorption capacity (mg.g1)

qt amount of ions adsorbed at given timet(mg.g1)

te time of equilibrium

Xm adsorption capacity (mol.g1)

M. Balaz e t al. / Chemosphere 146 (2016) 458e471 459


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The milling ran in batch mode, so for each experiment, a newsample was provided.

2.3. Characterization

2.3.1. Specic surface area measurements

The specic surface area was determined by the low-

temperature nitrogen adsorption method using NOVA 1200e Sur-

face Area & Pore Size Analyzer (Quantachrome Instruments, United

Kingdom). The values were calculated using the BET theory.

2.3.2. Infrared spectroscopy

The infrared spectra in the frequency range 4000e650 cm1

were obtained by using a FTIR spectrometer Tensor 29 (Bruker,

Germany) by applying the ATR method.

2.3.3. Scanning electron microscopy

The morphology of the samples was analyzed using a MIRA3 FE-

SEM microscope (TESCAN, Czech Republic) equipped with the EDX

detector (Oxford Instrument, United Kingdom). The majority of the

ESM samples were coated with the layer of carbon in order to

eliminate their undesirable charging.

2.3.4. Zeta potential

The zeta potential was measured using a Zetasizer Nano ZS

(Malvern, United Kingdom). For each measurement, 10 mg of ES/

ESM was put into 10 mL of distilled water or metal (Ag, Cd or Zn)

nitrate solution with the concentration of 200 mg L1. The mea-

surement was conducted within the pH range 2e13, which wasadjusted by the addition of 0.1 M HNO 3or 0.1 M NaOH.

2.4. Adsorption and desorption tests

The adsorption ability of the ESM was investigated on model

solutions of chemically pure AgNO3, Cd(NO3)2.4H2O and

Zn(NO3)2.6H2O in distilled water with the desired concentration.

The adsorption of silver(I) ions was pursued in the concentration

range 10e200 mg L1 and for the cadmium(II) ions, the range

10e150 mg L1 was examined. For the zinc(II) adsorption, only the

concentration 200 mg L1 was used. The adsorbent concentration

w a s 1 g L 1. The adsorption experiments were performed in

Erlenmeyer's asks placed on a laboratory shaker for a different

time (until the equilibrium was reached) at a laboratory tempera-ture. The pH was adjusted by the addition of 0.1 M HNO3 or 0.1 M

NaOH into the solution. The solutions were then ltered through

the lter paper and the ltrate was analyzed with respect to the

content of residual metal ions using an atomic absorption spec-

trometer SPECTRAA L40/FS (Varian, Australia).

The adsorption ability of the ES toward Ag(I) was investigated

using the same experimental setup as described for the ESM. The

effect of milling was investigated on a model solution of Ag(I) ions

with the concentration of 200 mg L1. For the adsorption at

different concentrations, the concentration range between 10 and

150 mg L1 was used. The adsorption of Ag(I) from waste was

performed using the ES sample milled for 360 min and the kinetics

of the process was studied by measuring the amount of adsorbed

silver(I) ions in different adsorption times (1e

240 min).

In the case of the desorption tests, the selected metal-ladensamples after the adsorption process were dried and separated

into three fractions. The samples were then put into distilled water

(the amount of used water was such that the concentration of the

metal-laden ESM was 1 g L1) and mixed for different time (30,120

and 360 min). After this process, the suspension was ltered

through the lter paper and the ltrate was analyzed in the same

way as in the case of adsorption tests.

3. Results and discussion

The industrial eggshell waste comprises two components-the

eggshell (ES) and the eggshell membrane (ESM). As enough

attention was devoted to the characterization and adsorptionability of the milled ES in our previous studies (Balazet al., 2013c,

2015a,2015b), the effect of milling was investigated in detail only

for the ESM.

The unique brous structure of the ESM is the most important

characteristics for its potential applications (Balaz, 2014). There-

fore the effect of high-energy milling (HEM), during which nor-

mally high milling velocities (e.g. 500e800 rpm) are applied,

would be most probably negative, as the unique brous structure

would be certainly destroyed. Because of that, we applied very

mild milling (100 rpm) and we hoped that the brous structure

would be maintained, at least to some extent. We hypothesized

that such a slight mechanical activation (Balaz, 2000) could

possibly enhance the properties of the ESM, namely the adsorption

ability toward heavy metal ions, as it was achieved in the case ofthe ES (Balazet al., 2015a). Our hypothesis was supported by the

work by Ishikawa et al. (2002), in which the positive effect of

powdering of the ESM was denitely conrmed. The impact of

mild milling on the ESM was pursued by the specic surface area

measurement, IR spectroscopy and SEM. Namely the ESM milled

for 30 min (labeled ESM30) was compared with the non-milled

ESM (ESM0).

3.1. Comparison of the physico-chemical properties between the

non-milled and milled ESM

3.1.1. Specic surface area measurements

The value of the specic surface area SA 13.2 m2

.g1

of thenon-milled ESM is signicantly higher than in the case of the non-

treated eggshell (0.5 m2.g1 (Tsai et al., 2008)), thus suggesting the

richer pore properties of the ESM. TheSAvalue was changing with

the time of milling. However, it did not increase, as in the case of the

eggshell (Balazet al., 2015a), but the decrease was observed. From

the initial value, it decreased to 2.4 m2.g1 after 5 min of milling

and further decrease to 0.7 m2.g1 was evidenced for the sample

ESM30. This is understandable, since the ESM can be categorized as

high-dispersed solid and the aggregation processes may prevail

over the dispersion even under mild milling (Sydorchuk et al.,

2010). When soft materials are treated, the energy is absorbed in

deformation processes (Butyagin, 1989), which is also the case of

the ESM. As the bers are mangled during milling, the surface is

signi

cantly compressed, which results in the reduced SAvalue.

Table 1

Different milling conditions used for treatment of eggshell and eggshell membrane.

Biomaterial Sample mass [g] Milling time [min] Milling speed [min1] Ball-to-powder ratio

ES 5 0e360 500 72

ESM 3 0e30 100 120

M. Balaz et al. / Chemosphere 146 (2016) 458e471460


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3.1.2. Infrared spectra

In order to determine, whether chemical changes take place

during the milling, the infrared spectra of the samples ESM0 and

ESM30 were recorded. They are presented inFig. 1.

The infrared spectrum of the ESM can be divided into two

regions-therst one between 3750 cm1 and 2500 cm1 and the

other one below 1700 cm1. In the region with higher wavelengths,

the most intensive peak is evidenced at 3287 cm1, which corre-

sponds tothe stretching mode of NeH bonds (Rath et al., 2014). The

peaks at 3060 cm1, 2932 cm1, and 2869 cm1 correspond to the

asymmetric stretching vibrations of the CeH bonds present

in CeH and CH2 groups (Kaiden et al., 1987; Weymuth et al.,

2010). In the region with lower wavelengths, the peaks at

1630 cm1 (C]O), 1530 cm1 (CeN stretching/NeH bending

modes), and 1234 cm1 (CeN stretching/NeH bending modes) can

be assigned to the amide I, amide II, and amide III vibrations of the

glycoprotein mantle of the bers, respectively (Bandekar, 1992;

Arami et al., 2006; Dong et al., 2007; Kong and Yu, 2007). The

peaks at 1448 cm1, 1073 cm1 and 620 cm1 correspond to the

stretching modes of C]C, CeO and CeS bonds, respectively (Dong

et al., 2007; Gunasekaran and Sailatha, 2008; Liu et al., 2008; Zhao

and Chi, 2009; Whitehead et al., 2011).

It can be seen that all the mentioned peaks are present in thespectra of both ESM0 and ESM30, so no chemical changes occur as a

result of mild milling. The only difference is the presence of small

double peak around 2350 cm1 in the spectrum of ESM30, which is

a result of the vibrations of the adsorbed molecules of atmospheric

CO2, but this has nothing to do with potential chemical changes in

the ESM.

3.1.3. Zeta potential

In order to check whether or not milling caused the changes in

the charge of the surface layer of the ESM, zeta potential values at

different pH for the samples ESM0 and ESM5 are compared in Fig. 2

below.

It can be seen from the gure that milling did not bring about a

signicant change in the value of ZP, so also the surface charge

distribution should be more-or-less maintained after the mild

milling, which further conrms that no chemical changes occur in

the ESM during this procedure.

3.1.4. Scanning electron microscopy

Milling denitely affects the morphology of the ESM. It could be

seen with the naked eye that the ake-like structure, which was

present before milling was maintained also in the case of the milled

samples, only the akes seemed smaller in the latter case. By the

means of SEM, the effect of mild milling on the morphology of the

bers of the ESM was investigated (Fig. 3).

Although the gures are of different quality due to the different

sample preparation, the differences can denitelybe seen. Whereas

inFig. 3a, the long non-touched bers of various diameter can be

observed, the mangled and crushed bers are visible inFig. 3b. It is

a proof that during milling, the bers are exposed to various forces,

causing them to deform and then lead to their rupture andcompression into circle shapes. InFig. 3b, two different morphol-

ogies can be observed. Whereas in the upper right part, the surface

layer of theake can be seen and no individual bers can be further

distinguished, in the lower left part, the residues of the torn bers

can still be observed. For better understanding, the magnied SEM

images of both these regions were recorded (Fig. 4).

InFig. 4a, where the residues of the bers from the bulk of the

ake are shown, the effect of milling is not so pronounced. Some

bers maintained their structure, although there are small lumps

present on them. In the upper part, it seems that one ber is

starting to be wrapped by the residues of some other bers. Maybe

this is the mechanism how the surface lump-like layer, the

morphology of which is shown in Fig. 4b, is formed. The lumps at

this surface layer are of various sizes, so it is possible that rstly the

small ones are formed and as the milling proceeds, they are getting

larger, as more residues of the bers are incorporated into them. No

bers can be observed at the surface of the ake, as the milling balls

have totally destroyed the original morphology there.

3.2. Adsorption of heavy metal ions on the ESM

The ESM was used for the adsorption of three selected metal

ions from their water solutions (namely cadmium(II), silver(I) and

zinc(II)).

3.2.1. Optimization of pH

Firstly, zeta potential was measured, in order to determine the

most suitable pH value for the adsorption. The dependences of ZP

Fig. 1. The infrared spectra of the ESM: black lineenon-milled; red lineemilled for

30 min. (For interpretation of the references to colour in this gure legend, the reader

is referred to the web version of this article.)

Fig. 2. The inuence of milling on zeta potential: the dependence of zeta potential on

the pH for ESM0 and ESM5.



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on pH for all three ions are presented inFig. 5aec.

It can be seen that in all the studied cases, excluding the area of

high pH values for Ag(I) adsorption (right part ofFig. 5a), a shift

toward the positive values of zeta potential was observed after

immersing the ESM into all studied metal ion solutions. This is aconsequence of the presence of larger amount of positively charged

metal ions near the surface of the sorbent. The pH, at which the

largest difference between the ZP values of ESM in water and in

corresponding salt was recorded was considered optimum. How-

ever, as in the case of Cd(II) (Fig. 5b) and Zn(II) (Fig. 5c), it was pH 8

and there would be a danger of the precipitation of metal hy-

droxides (Chen, 2010), pH 7 was applied for these two ions. For

Ag(I), pH 6 was satisfactory (Fig. 5a).

3.2.2. Selectivity tests

After the determination of the most appropriate pH, the

adsorption tests for all three ions were performed with the non-

milled ESM. The adsorption ability (represented by the value qt)

toward each ion is shown in Fig. 6.

It can be seen from the gure that the ESM exhibits a selectivity

towards different ions, thus conrming the facts presented in

Ishikawa et al. (2002). It was found that the adsorption ability of the

non-treated ESM toward cadmium(II) lies in between the ones

toward silver(I) and zinc(II) ions. The adsorption ability towardsilver(I) is the highest, while zinc(II) is not adsorbed. It was

concluded that the ESM is not capable of Zn(II) ions adsorption, so

further considerations in the paper are related only to the

adsorption of silver(I) and cadmium(II) ions.

3.2.3. Inuence of milling

The inuence of mild milling was evaluated for the adsorption

of Ag(I) and Cd(II) ions. The results are presented inFig. 6.

It can be seen from the gure that mild milling has a negative

inuence on the adsorption ability, unlike in the case of the

eggshell (Balaz et al., 2015a). In the case of Ag(I) (Fig. 7a), this

negative inuence becomes evident after 5 min of milling, whereas

in the case of Cd(II) (Fig. 7b), it takes longer time to express. It

becomes signi

cant after 30 min of milling. These results did not

Fig. 3. The SEM images of the samples: (a) ESM0; (b) ESM30.

Fig. 4. The SEM images of the sample ESM30: (a) thebers inside the ake; (b) the surface of the ake.



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support our hypothesis about the improved adsorption ability as a

result of milling based on the positive effect of particles miniatur-

ization reported inIshikawa et al. (2002). It is highly probable that

the active sites were destroyed despite the application of very mild

milling in our case. On the other hand, cutting and minimizing the

particle size by the laboratory blender performed within the work

(Ishikawa et al., 2002) most probably did not affect the structure of

the active sites, only exposing more of them, thus resulting in

higher adsorption ability. Nevertheless, although milling did notbring about the improvement of the adsorption ability of the ESM,

the non-milled ESM was investigated further.

3.2.4. Adsorption isotherms

The adsorption isotherms for the adsorption of Ag(I) and Cd(II)

on the non-treated ESM are shown in Fig. 8.

The shape of the adsorption isotherms for two studied ions in

the studied concentration range is different. Whereas for Ag(I), a

plauteau can be observed for concentrations higher than 80 mg L1,

in the case of Cd(II), more-or-less constant increase of the

adsorption ability as the concentration increases can be observed.

These results hint to the potential different mechanism of the

adsorption.

3.2.5. Comparison of Langmuir and Freundlich parameters

These data were used for the evaluation of the Langmuir and

Freundlich parameters. The linearized forms of Langmuir and

Freundlich isotherms were applied (Eqs. (1) and (2), respectively).

Ceqe

1

Qmb

CeQm

(1)

where ceand qeare the equilibrium solute concentration [mg.L1]

and the equilibrium adsorption capacity [mg.g1], respectively,Qmis the Langmuir constant representing the maximum monolayer

adsorption capacity (amount of adsorbed metal ions per 1 g of

sorbent as a monolayer) and b is the constant of the Langmuir

Fig. 5. The dependence of zeta potential on the pH for ESM in water (black) and in corresponding metal nitrate solution (red): (a) Ag; (b) Cd; (c) Zn (cM 200 mg L1). (For

interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 6. The adsorption of Ag(I), Cd(II) and Zn(II) ions on the non-milled ESM

(cM 200 mg L1 pHAg,Zn 6, pHCd 7).



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isotherm related to the heat of adsorption [L.mg1].

lncs lnKf nf lnce (2)

where cs is the amount of the adsorbedmetal ion [mol.g1]; ce is the

equilibrium solution concentration of metal ion [mol.L1];Kfis the

Freundlich constant [mol.g1], nf is a constant representing the

adsorption intensity of the adsorbent.

The results obtained by applying these models for both studied

ions and the corresponding parameters are presented below in

Fig. 9and Table 2, respectively.Interesting conclusions can be drawn from the gure and table.

Whereas for the adsorption of silver(I), the Langmuir model is more

suitable, the Freundlich model is more suitable for cadmium(II)

adsorption. This is, of course, connectedwith the differentshapes of

the adsorption isotherms presented in Fig. 8. It is possible that

different mechanism is taking place for the adsorption of each ion.

InKoumanova et al. (2002), it is stated that the suitability of the

Langmuir model conrms the chemisorption, so it seems that silver

should be adsorbed non-reversibly. However, the correlation co-

efcient for the Langmuir model in the mentioned paper was only

0.76 and it was 0.85 for the Freundlich model, so it seems that the

latter model is more suitable also in their case. Nevertheless, our

results further conrm the selectivity of the ESM toward different

ions and the obtainedQmvalue, namely for the adsorption of Ag(I)

ions is comparable to other natural or modied biosorbents (Coruh

et al., 2010; Lihareva et al., 2013; Sari and Tuzen, 2013 ). In order to

elucidate the reversibility/irreversibility of the adsorption, the

desorption experiments were performed (part 3.4).

3.2.6. Characterization of products after adsorption

The ESM after the adsorption of Ag(I) and Cd(II) ions was

characterized by FTIR and SEM. No differences could be observed

before and after the adsorption of both ions in the FTIR spectra and

therefore, they are not provided. Also no hypothesis about the

particular functional groups of the ESM involved in the adsorption

can be stated.

Using the SEM microscopy, elemental mapping was performed

and EDX spectra were collected for the sample after the adsorption

of both ions. The results for the adsorption of Ag(I) and Cd(II) are

shown inFigs. 10 and 11, respectively. Carbon label was removed

from both gures (the sample was coated with it in order to avoid

unwanted charging by the electron beam), as it could cause some

confusion, if it was maintained within the results. However, the

main peaks of carbon can be seen in both EDX spectra (the most

intensive peaks).

3.2.6.1. Ag-laden ESM. In Fig. 10a, the EDS layered image

comprising all the elements is shown. The individual mapping for

O, S and Ag is presented in Fig. 10be

d, respectively. At the

rst

Fig. 7. The inuence of mild milling on adsorption ability of ESM toward: (a) Ag(I); (b) Cd(II) (cM 200 mg L1, pHAg 6, pHCd 7).

Fig. 8. The adsorption isotherms for metal ions adsorption on the ESM: (a) Ag(I); (b) Cd(II).



8/14

glance it seems that the mapping results are inconsistent, as the

distribution of individual elements differs signicantly. However, it

is known that the difference in the depiction of elemental distri-

bution is dependent on the atomic number and that the exact

localization of lighter elements is more precise than in the case of

heavy elements. Therefore it seems that oxygen is located exactly

on the bers, as it is the lightest element from the studied ones. On

the other hand, the adsorbed Ag is heavy element and therefore it

seems that its distribution is completely homogeneous and not

connected to the ESM bers at all. However, its presence in the

system is undeniable. In the EDX spectra (Fig. 9e), the same ele-

ments can be observed. These results represent the proof of the

successful adsorption of Ag(I) on the ESM.

3.2.6.2. Cd-laden ESM. The results for the cadmium(II) adsorption

are quite similar to the ones obtained for the adsorption of silver(I).

The homogeneous distribution of Cd, which can be seen mainly in

Fig. 11d can be explained by the same effect of heavy element

mentioned forsilver. The EDX spectrum in Fig. 11e looks also similar

as in the case of Ag(I) adsorption, however the amount of the

adsorbed metal, compared to silver is signicantly lower (in the

case of Ag, it was 27.9% and for Cd it is only 10.9%). The results arecomparable, as the values for the elements O and S are more-or-less

the same in both cases. The obtained results are in accordance with

the observations made from the adsorption tests, in which also the

larger amount of silver(I), in comparison with cadmium(II), was

adsorbed.

3.3. Desorption tests

In order to determine the stability of the ESM-metal ion system,

the desorption tests were performed. The results for both ions are

presented inTable 3.

It can be seen that the percentual amount of both desorbed

metals is low, however it slightly increases with the desorptiontime. The difference in the behavior of the two ions can be

observed.

The results with the desorption of Ag(I) have shown almost

negligible values of the desorbed metal within the rst two hours.

Although the higher value was observed in the case of the sample

desorbed for 30 min, the difference is within the range of a mea-

surement error. However, 3.5% desorbed Ag(I) after six hours

cannot be neglected. It seems that silver(I) ions are adsorbed quite

strongly on the ESM, so a possible chemical adsorption can take

place. However, as it partly leaks into water, the process cannot be

considered completely chemical, but in general it can be stated that

the desorbed values are low.

The results with the Cd-laden ESM have shown that a small

amount of cadmium(II) is released into the solution and in

Fig. 9. The linearized adsorption isotherms for the adsorption of metal ions on the ESM: (a) Langmuir, Ag(I); (b) Freundlich, Ag(I); (c) Langmuir, Cd(II); (d) Freundlich, Cd(II).

Table 2

The parameters for the adsorption of silver(I) and cadmium(II) ions on the ESMobtained by applying various models.

Ion Langmuir model Freundlich model

Qm[mg.g1] b[mg.g1] R2l KF [mmol.g

1] nf R2

f

Ag(I) 52.910 0.270 0.9956 4.468 0.314 0.9494

Cd(II) 23.419 0.037 0.9002 6.935 0.531 0.9974



9/14

comparison to Ag(I) release, the values are higher. The value after

6 h is 1.8-fold higher than in the case of Ag(I). It hints to the fact,

that the binding is weaker in the present case and that the potential

chemical adsorption is taking place to a smaller extent. Thus the

adsorption process cannot be considered irreversible, on the con-

trary to the adsorption of Cd(II) on the ES (Balazet al., 2015a). This

follows the different chemical composition of the ES and ESM.

In summary, it can be concluded that the desorption process

occurs in the case of both ions, and in comparison with other sor-

bents (Lata et al., 2015), the values are low. The process of irre-

versible adsorption is more signicant in the case of Ag(I), thus

supporting the hypothesis about the chemisorption based on the

better suitability of the Langmuir model. Of course, it can be hy-

pothesized that if the desorption time would be long enough, all

the adsorbed species would be desorbed, but we consider this

improbable, as the desorbed values after 6 h are low. However, no

Fig.10. Surface characterization of the ESM after the adsorption of Ag(I): (a) SEM with EDS layered image; elemental mapping: (b) oxygen; (c) sulphur; (d) silver; (e) EDX spectrum.

Fig. 11. Surface characterization of the ESM after the adsorption of Cd: (a) SEM with EDS layered image; elemental mapping: (b) oxygen; (c) sulphur; (d) cadmium; (e) EDX

spectrum.

Table 3

Results of desorption tests.

Desorption time [min] Desorbed amount of ion [mg L1]

Ag(I) Cd(II)

[mg.L1] [%] [mg.L 1] [%]

Adsorbed 59.7 e 11.3 e

30 0.65 1.09 0.15 1.33

120 0.43 0.72 0.33 2.92

360 2.09 3.50 0.71 6.28



10/14

denite conclusions can be made and further studies would be

necessary in order to elucidate the exactrole andshare of reversible

and irreversible adsorption.

3.4. Adsorption of silver(I) ions on eggshell

As the adsorption of silver(I) ions on the ESM was the best

among the studied heavy metal ions, we have decided to compare it

with the adsorption ability of the ES.

3.4.1. Optimization of pH

Tond out which pHwould be the most suitable for the sorption

of Ag(I) ions on the ES, the measurements of zeta potential at

different pH for the milled ES both in water and in silver nitrate

solution were carried out. The results are shown in Fig. 12.

The differences in the zeta potential values in the case of water

and silver nitrate solutions are obvious. The shift toward the more

positive ZP values was observed again in the presence of the salt

solution, similarly to the ESM. It can be seen from the gure that

both high and low pH are not suitable for the adsorption, as in the

rst case, AgOH starts to precipitate at pH between 7 and 8 (Chen,

2010) and in the latter case, the CaCO3 from the ES is signicantly

dissolved (Flores-Cano et al., 2013). The value of zeta potential at pH

5 in the water solution was 11.3 mV, whereas in the case of silver

nitrate solution, it was 3.8 mV. The difference between zeta po-

tential values in this case was the highest and therefore this pH was

selected for the sorption experiments.

3.4.2. Inuence of milling

The kinetics of the adsorption of Ag(I) on the ES was studied on

three selected ES samples. The results are presented inFig. 13.

As can be seen in the gure, the milling for 60 min did not bring

about the increase of the adsorption ability at all, as the results for

the non-treated sample and the sample milled for 60 min were

almost identical- the amount of the adsorbed silver(I) ions was

around 40 mg.g1 for both samples. The sorption process was

very fast, because the values of Ag(I) uptake were almost the samefrom the rst measurement after 5 min and did not vary much as

the sorption progressed. On the other hand, milling for 360 min

lead to a signicant effect- more than two-fold increase in sorption

ability was observed. This could be in connection with the

increasing amount of aragonite phase in the milled ES, as its in-

uence was denitely conrmed in the case of cadmium and was

discussed in detail inBalazet al. (2015a). It is possible that calcite

itself is not a good adsorbent of Ag(I), while aragonite is (Demina

et al., 2012). According to Balaz et al. (2015a), there is 7.5%

and 54.9% aragonite in the ES milled for 60 min and 360 min,

respectively, so it is possible that some critical amount of aragonite

phase necessary for the improved adsorption ability toward sil-

ver(I) ions to show. The change in the values of the specic surface

area is not a key parameter, similarly as in the case of cadmium(II)

adsorption.

3.4.3. Adsorption isothermsTo calculate the maximum adsorption capacity of the ES milled

for 360 min, the experiments with different concentrations were

performed. According to the kinetics study, the sorption time of

240 min seemed appropriate. The adsorption isotherm is shown in

Fig. 14.

The shape of the isotherm is quite similar to that of the

adsorption of Ag(I) ions on the ESM, with a plateau in the area of

higher concentrations.

Fig. 12.The dependence of the zeta potential of the sample ES360 on pH in water and

in silver nitrate solution (cAg

200 mg L

1

).

Fig. 13. The inuence of milling time on the adsorption ability of ES towards Ag(I)

(cAg 200 mg L1, pH 5).

Fig. 14. The adsorption isotherm for Ag(I) ion adsorption on the sample ES360.



11/14

3.4.4. Comparison of Langmuir and Freundlich parameters

The obtained dependance was linearized by applying both

Langmuir and Freundlich models. The linearized curves and the

corresponding parameters are summarized inFig. 15andTable 4.

It can be seen from the results that Langmuir model accurately

describes the process, while Freundlich model does not. From our

point of view, the obtained value of maximum adsorption capacity

55.7 mg.g1 is high enough to be interesting for further environ-

mental applications.

3.4.5. Adsorption of Ag(I)-containing waste

To show the application potential of the milled ES in technology,

the adsorption tests on the technological waste containing silver(I)

were performed, using the sample ES360 (sample with the best

results in the kinetic study). The concentrations of all cations

detected in the waste are presented inTable 5.

It can be seen that the major component of the waste is chro-

mium. Potassium, silver and zinc are almost of equal amount, all

being present in tens ofmg.mL1. Also the contribution of another

minor constituents present in the ng.mL1 scale cannot be

neglected. The adsorption of chromium on the ES was investigatedrecently (Daraei et al., 2015; Kumaraswamy et al., 2015) with

the conclusion that chromium can be effectively adsorbed. There-

fore its vast abundancy in the present waste might be of great

signicance and certainly affects the adsorption of silver(I). A

signicant amount of potassium and zinc would also denitely

inuence the adsorption ability of the ES, representing the candi-

dates for the potential competition for the active sites. Despite

all these facts, only the adsorption of silver(I) was pursued in order

to compare the results with the Ag(I) adsorption from the model

solution.

The results of sorption kinetics are presented inFig. 16below.

It can be seen from the gure that almost half of Ag(I) ions

present in the waste (the measuredqtvalue was 28.59 mg Ag(I)/g

ES) was adsorbed immediately (after 1 min) by the milled ES andthis amount did not vary much with the increasing sorption time.

However, slight increase was evidenced in the case of longer

adsorption times. The nal qtvalue after 240 min was 37.41 mg

Ag(I)/g ES. The lower value in comparison with the model solutions

can be explained by the presence of other ions in the waste, which

compete for the adsorption sites with the Ag(I) ions. However, the

possibility of utilizing the ES biomaterial for the industrial appli-

cation is denitely conrmed.

3.5. The comparisons

Within this study, a lot of collected data can be compared by

Fig. 15. The linearized adsorption isotherms for the adsorption of Ag(I) on the sample ES360: (a) Langmuir; (b) Freundlich.

Table 4

The parameters for the adsorption of silver(I) on the sample ES360 obtained by

applying various models.

Langmuir model Freundlich model

Qm [mg.g1] b[mg.g1] R2l Kf [mmol.g

1] nf R2

f

55.7 0.68 0.9983 2.203 0.192 0.7470

Table 5

The cations present in waste.

Major cations Concentration [mg.mL] Minor cations Concentration [ng.mL]

Cr 481.3 Fe 345

K 62.9 Mn 236

Ag 54.71 Al 66

Zn 45.7 Na 14

Ni 10

Pb 5

Cu 5

Co 0.5

Fig. 16. The adsorption of Ag(I) by the sample ES360 from the technological waste.



12/14

selecting different criteria, thus suggesting interesting conclusions.

They key data for these comparisons, being the zeta potential and

Qmvalues, are presented inTable 6below.

3.5.1. Zeta potential of the two biomaterials

The zeta potential value for the ES360 in water is much less

negative than in the case of the ESM0 at the pH selected for theadsorption. This is the result of smaller amount of charged groups

present on the surface of the ES. The values in the presence of sil-

ver(I) ions are also signicantly lower for the ES. The difference in

the zeta potential values in water and in silver(I) salt is signicantly

higher for the ESM, therefore predetermining it to be a better

adsorbent of the Ag(I) ions.

In the case of Cd(II) ions, the ZP value for the ESM is even more

positive than in the case of Ag(I). This phenomenon could be

possibly connected with the more positive charge of Cd(II) ion. The

ZP value for the ES360 was not recorded in the previous work and

therefore cannot be compared with the value of ESM0.

3.5.2. Non-treated adsorbentsThe non-milled materials exhibit different afnity toward the

studied ions. In the work by Ho et al. (Ho et al., 2014) the values for

ES, ESMand the material composed of both these components were

compared with the result that the ESM is the best adsorbent. In the

present work, the maximum adsorption capacity 52.91 mg g1 for

the non-treated ESM is evidenced, whereas for the pre-milled ES

(ES0), the obtained qe value (as the Qm was not calculated) is

38.7 mg g1. It can be therefore concluded that ESM is a better

adsorbent for the Ag(I) ions than the ES, thus conrming the results

by Ho et al. It has to be stressed out, that ES0 sample used in the

present study was pre-milled and therefore cannot be considered

natural adsorbent. It is highly probable that the qe value of the

natural ES would be signicantly lower than the value of ES0.

Considering the adsorption of cadmium(II), the Qm value23.419 mg g1 was evidenced for the ESM0. Koumanova et al.

(Koumanova et al., 2002) reported this value to be 24.27 mg g1, so

the results are very close. However as the Langmuir model does not

t well in either of these studies, it is probably better to consider

the value qe equal to 14.7 mg g1 in further comparisons. If the

Freundlich parameters are considered, Kfvalue 6.935 mmol g1 was

evidenced, whereas inKoumanova et al. (2002), it was signicantly

higher- 32.49 mol g1. However, in the present case we have re-

ported almost idealt of the Freundlich model for the adsorption of

the Cd(II) on the ESM, whereas in the paper (Koumanova et al.,

2002), R2 was only 0.85 and moreover, it has to be kept in mind,

that there are always some experimental differences when

comparing the values form different works, which could signi-

cantly alter the results. If the above-mentioned q e value obtainedfor the ESM is compared with the natural ES (in Flores-Cano et al.

(2013)) it was reported to be up to 4 mg g1), it can be concluded

that the natural ESM is a better adsorbent also for the Cd(II) ions.

3.5.3. The effect of milling

It can be seen fromthe resultsthatmillinghas a different impact

on both studied biomaterials. It was shown earlier in this paper that

it has more-or-less negative inuence on the ESM, however it

signicantly improves the adsorption ability of the ES. In the case of

Ag(I) adsorption, theqevalue for the pre-milled ES is 38.7 mg g1,

and by the application of the long-term milling, it is possible to

increase its adsorption ability to more-or less the same level as it is

for the natural ESM (the value 55.7 mg g1 is evidenced for the

sample ES360). For the cadmium(II) adsorption, only slight pre-

milling (sample ES0) turns the ES into better adsorbent than the

natural ESM (qevalue 48.1 mg g1 was evidenced). The adsorption

ability becomes even more signicant as the milling time increases

(Balazet al., 2015a).

3.5.4. The afnity toward Ag(I) and Cd(II) ions

The two studied biomaterials seem to behave differently toward

the two ions. As can be seen fromTable 2, the ESM exhibits almost

two-fold higher afnity toward Ag(I) in comparison with Cd(II) ion,

as is documented by the higher Qm and Kfvalues. As the atomicradii

of the two atoms are quite similar, the different behavior is prob-

ably connected with the charge of the ions. It seems that lower

charge seems to be more suitable for the ESM. This could bepossibly proved in the future by the experiments with the

adsorption of different metal(I) ions on the ESM.

As for the ES, we did not study the behavior of the natural

biomaterial. The pre-milled and milled ES were studied in detail.

Theqevalue for the ES0 sample is 38.7 mg g1 and 48.1 mg g1 for

the Ag(I) and Cd(II) ions, respectively, suggesting the higher afnity

of the ES toward Cd(II) ions. By the application of milling, this dif-

ference becomes even more signicant (see the values for the

ES360 sample in Table 4). The higherafnity of the ES toward Cd(II)

ions could possibly connected with the similarity in the charge

between the Ca(II) and Cd(II) ions, which could be possibly inter-

changed. However, this was studied in detail in other works(Flores-

Cano et al., 2013; Balazet al., 2015a). There is one last phenomenon

to be discussed in the case of the milled ES in relation to theadsorption ability toward Ag(I) and that is the calcite-aragonite

phase transformation occurring during milling. It was discussed

in detail in relation to the adsorption of Cd(II) ions in our recent

work (Balazet al., 2015a). According to the paper (Demina et al.,

2012), it seems that the aragonite phase exhibits higher afnity

toward Cd(II) than toward Ag(I), which is conrmed also in this

study for the milled ES (sample ES360 contains 54% aragonite)

(Balazet al., 2015a).

4. Conclusions

In the present paper, the adsorption behavior of both compo-

nents of the eggshell waste, namely the eggshell (ES) and the

eggshell membrane (ESM) was compared with the focus on theinuence of milling.

Firstly, mild milling was applied on the ESM, in order to partly

maintain its brous structure with the aim to potentially increase

its application potential. No changes were observed in the infrared

spectra after milling, being the proof that no chemical changes

occurred within the process. The values of the specic surface area

decreased dramatically in the rst 5 min of milling, while further

milling brought about only a slight decrease, thus documenting the

gradual deterioration of the brous structure. The SEM images of

the ESM milled for 30 min showed the two types of morphology

(the residues of the bers at the surface layer and more-or-less

maintained brous structure in the bulk layer).

The adsorption ability of the ESM toward cadmium(II), silver(I)

and zinc(II) ions was also investigated. According to zeta potential

Table 6

The zeta potential andQmvalues for the studied adsorbents and ions.

Ion Zeta potential [mV] Qm[mg.g1]

ESM0 ES360 ESM0 ES360

e 31.5 (pH 6, Ag(I))

38.5 (pH 7, Cd(II))

11.3a e e

Ag(I) 17.9 3.8a 52.910 55.7

Cd(II) 43.3 e 23.419 488.82a

a

This value is taken from the paper ( Bal

a

zet al., 2015a).



13/14

measurements, the optimum pH for the adsorption of Ag(I), Cd(II)

and Zn(II) ions were 6, 7 and 7, respectively. The ESM exhibited a

selectivity toward different ions. The zinc(II) ions were not adsor-

bed at all. The cadmium(II) ions were adsorbed to small extent and

the afnity of the ESM toward silver(I) ions was by far the highest. It

was shown that milling did not bring about any improvement in

the adsorption ability of the ESM. The adsorption of Cd(II) and Ag(I)

on the ESM was evaluated using the Langmuir and Freundlich

models. Whereas the former one was more suitable for the

adsorption of Ag(I), the latter for Cd(II), thus suggesting different

mechanisms of adsorption. The calculated value of the maximum

adsorption capacity according to Langmuir model was 52.9 and

23.4 mg g1 for Ag(I) and Cd(II) ions, respectively. The presence of

both adsorbed species on the ESM was conrmed by elemental

mapping and EDX measurements. The desorption experiments

have shown the difference in the stability of the Ag- and Cd-laden

ESM. Although both ions slowly leak into the distilled water, the

process is more pronounced for Cd(II), thus conrming the poten-

tially lower share of the irreversible adsorption, compared to Ag(I).

The adsorption of Ag(I) ions was tested also on the ES. The zeta

potential measurements revealed that the ideal pH for the

adsorption tests was 5. On the contrary to the ESM, milling brought

about the increase of the adsorption ability of the ES toward Ag(I)ions, although 60 min of milling was not enough. However when

the duration of milling was extended to 360 min, the adsorption

ability was increased signicantly. This is most probably connected

with the large amount of aragonite phase in the system. The

Langmuir model was proved to be suitable to describe the

adsorption process and the Qmvalue 55.7 mg g1 was calculated.

The possibility of applying milled ES in technology was demon-

strated on the adsorption of silver(I) from the technological waste,

where almost half of silver(I) ions were successfully adsorbed on

the ES.

In the last part, various comparisons were outlined with the

general conclusion that the eggshell biomaterial is very interesting

in the terms of the selectivity. Whereas the ESM exhibits higher

afnity toward Ag(I) ions, the situation is the other way round inthe case of the ES. The milling makes the ES more efcient adsor-

bent than the ESM, favoring the adsorption of Cd(II) over Ag(I) ions.

In general, the obtained results, namely the Qmvalues obtained

for the adsorption of Ag(I) ions are comparable to many other

natural or modied biosorbents. We tried to show within this work,

that the eggshell waste is very interesting for the potential appli-

cations for the wastewater treatment and is worth much more than

just a space in the trash can.

Acknowledgments

This work was supported by the Slovak Research and Develop-

ment Agency under the contract No. APVV-14-0103. The support of

other projects, namely Centre of Excellence of Slovak Academy ofSciences (project CFNT-MVEP), Slovak Grant Agency VEGA (projects

2/0027/14, 2/0051/14 and 2/0097/13) and European Regional

Development Fund (projects nanoCEXmat I (ITMS 26220120019)

and nanoCEXmat II (ITMS 26220120035)) is also gratefully

acknowledged.

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Influencia de La Molienda Sobre Adsorción de Los Residuos de Cáscara de Huevo

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