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Ecological Engineering 88 (2016) 82–89

Contents lists available at ScienceDirect

Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Cerastoderma lamarcki shell as a natural, low cost and new adsorbent


to removal of dye pollutant from aqueous solutions: Equilibrium and
kinetic studies
Sayed Yahya Kazemi a,∗ , Pourya Biparva a , Elham Ashtiani b
a
Department of Basic Sciences, Sari Agricultural Sciences and Natural Resources University, PO Box 578, Sari, Iran
b
Department of Marian Science, University of Mazandaran, Babolsar, Iran

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

Article history: The readily available, highly efficient and relatively inexpensive adsorbents of Cerastoderma lamarcki shell
Received 14 April 2015 (CLS) was applied for removal of dye as pollutant using the Taguchi design as an optimization strategy.
Received in revised form The Taguchi design was utilized to find out the influencing optimization conditions. As expected, the C.
24 November 2015
lamarcki waste shell is mainly composed of mineral component, so powdered CLS applied for removal of
Accepted 8 December 2015
dye pollutant. The pH of solution, CLS particle size, adsorbent dose, contact time, temperature and initial
Available online 24 December 2015
dye concentration were studied as the affecting factors on the adsorption process. The experimental
results showed that maximum adsorption occurs in pH about 5. The equilibrium was attained for dyes in
Keywords:
Pollutant
60 min. Adsorption isotherm well fitted to the Freundlich and kinetics of the adsorption reaction followed
Cerastoderma lamarcki shell the pseudo second-order. The maximum adsorption capacity for malachite green was 35.84 mg/g at
Adsorbent 303 K. The morphology of the surface of adsorbent was studied before and after the adsorption by SEM
Malachite green micrograph. It was concluded that CLS powder has a great potential to be applied as an adsorbent for
Taguchi design removal of malachite green.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction removal of dyes from wastewater such as agricultural residues


(Nigam et al., 2000), dolomitic (Walker et al., 2003), fly ash(Eren
It is clear that environmental pollution is a global issue. Dyes and Acar, 2007) zeolite (Wu et al., 2006), chlorella (Tsai and
are of the most harmful chemical compounds present in industrial Chen, 2010), sewage sludge ash (Pan et al., 2003). The successful
sewages causing decrease in light penetration and perturbation in use of marine adsorbents such as: Sea shells (Chowdhury and
photosynthesis process in water sources. Dyes can pollute drinking Saha, 2010), oyster shells (Liu et al., 2010), mussel shells (Haddad
water (Royer et al., 2010), cause allergy, irritation (Brookstein, et al., 2014) and scallop (Siboni et al., 2014) have also been
2009), cancer disease (Lima et al., 2007) and mutations (Carneiro reported. Since, marine adsorbents are available and inexpensive
et al., 2010), thus removal of dyes as a pollutant is an interesting can potentially be applied to remove dye pollutants from queues
subject (Royer et al., 2009; Lima et al., 2008). There are many solution.
approaches for water purifying such as: oxidation (Karatas et al., These materials are utilized in many processes including sulfur
2012), reverse osmosis, membrane filtration (Wu et al., 1998), adsorbing (Jung et al., 2000), removal of phosphate (Namasivayam
chemical precipitation (Zhu et al., 2007), ion exchange electrolysis et al., 2005), metallic ion trapping (Blais et al., 2003), material syn-
(Raghu and Basha, 2007) and adsorption (Eren and Acar, 2006). thesis (Yoon et al., 2004), sludge removal (Lee et al., 2001) and food
Most of these techniques, however, suffer from several drawbacks, preservatives (Kim et al., 2007). Cerastoderma lamarcki shell (CLS)
including the requirement of high operational cost, high energy is selected as a suitable material for water pollutants removing. C.
and reagent, insufficient selectivity and incomplete dye removal, lamarcki is a type of marine organism, which is a part of the Ceras-
but adsorbing technique is effective due to its simplicity and toderma Genus (Subfamily of Lymno cardiinae). C. Genus is in the
reproducibility (Tsai et al., 2009). There is, therefore, considerable Cardiidae Family and Cardioidea Superfamily, the Veneroida Order
interest in developing the use of low-cost adsorbents for the (Birshtain et al., 1968). When the animal died, Shells are washed
up onto a beach empty and clean. Shells are made up of three sep-
arate layers: cuticle, prismatic and nacreous. The prismatic layer
∗ Corresponding author. Tel.: +00 98 113 368 7655; fax: +00 98 113 368 7567. has a large number of micropores (Namasivayam et al., 2005; Hsu,
E-mail address: sykazemi@gmail.com (S.Y. Kazemi). 2009) which are the rich source of calcium carbonate. Reusability

http://dx.doi.org/10.1016/j.ecoleng.2015.12.020
0925-8574/© 2015 Elsevier B.V. All rights reserved.
S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89 83

Fig. 1. The images of Cerastoderma lamarcki samples.

and abundance of C. lamarcki compared to other adsorbents is its


main advantages.
The selection of a suitable adsorption condition is crucial for the
removal of the pollutant, so it is important to determine the vari-
ables influencing the removal percent. The conventional method
for medium optimization is “one at a time” approach that is time
consuming, expensive and unmanageable (Kazemi et al., 2010,
2014; Zolgharnein et al., 2008). A large number of variables have
to be investigated in designing a new adsorption condition and
measurement conditions such as pH, temperature, reaction time,
amount and the size of adsorbent on the dye adsorption. Mul-
tivariate optimization through experimental design has several
advantages rather than traditional method not only for having
fewer experiments but also to present more information about
the whole process under consideration. The information would be
summarized on the recognition of effective variables interaction,
and finding a mathematical model. Owing to this, the relation of
percent removal of dye to variables and their interactions and find-
ing optimum conditions for best performance of removal would be
achievable as well (Kazemi et al., 2010, 2014; Zolgharnein et al.,
2008).
In this study we investigated the potential of CLS to remove
malachite green (MG) from aqueous solution. The influence of pH,
temperature, reaction time, amount and size of adsorbent on the
dye adsorption was investigated. The Taguchi design was utilized
to find out the influencing optimization conditions. Also adsorption
Fig. 2. (a) Natural form of CLS SEM without contact with dye solution, (b) SEM
isotherm and kinetic studies were performed to find the adsorption
(image size 10 ␮m) of CLS after contact with dye solution, and (c) SEM (image size
mechanism and efficiency of CLS. 1 ␮m) of CLS after contact with dye solution.

2. Materials and methods


using scanning electron microcopies LEO 1455 VP (Zeiss,
2.1. Cerastoderma lamarcki shell sample Oberkochen, Germany). The SEM image of the adsorbent before
contact with dye solution is presented in Fig. 2a; and the SEM
Cerastoderma lamarcki were collected from the Caspian Sea images after contact with dye solution are shown in Fig. 2b and c.
beach in Sari, Iran (Fig. 1).CLS were washed twice with double
deionized water and then dried at 85 ◦ C for 12 h in oven to remove 2.2. Chemical and reagent
moisture. CLS were crushed, powdered to small grains using a
hammer mill into small particles of different sizes in the range All chemicals were analytical grades and solutions were pre-
of 74–425 ␮m. The morphology of the adsorbent was investigated pared with double deionized water from a hydroservice reverse
84 S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89

Fig. 3. The structure and characteristics of Malachite green.

osmosis-ion exchange apparatus. Malachite green (MG) was pur- The optimization of obtained results was analyzed using MINITAB
chased from Merck (Darmstadt, Germany). The chemical structure, 16 for windows. (Daneshvar et al., 2007; Ross, 1996; Moghaddam
properties and absorption spectrum of Malachite green have been et al., 2006)
presented in Fig. 3. MG is an extensively used biocide in the aqua-
culture industry world-wide and is also as a medical disinfectant 3. Result and discussion
(Chowdhury et al., 2010; Saha et al., 2010). The initial pH of solution
was adjusted by the addition of 0.01 M NaOH and 0.01 M HCl and All experiments were done as: 50 mL of MG solution added to the
measured by pH meter (Metrohm, Switzerland) 1 g of CLS in a100 mL Erlenmeyer flask and UV–vis spectrophotome-
ter was used to study the adsorption performance under different
2.3. Adsorption experiments experimental conditions. All the r results show the percent of the
adsorption of dye in the surface of CLS.
The equilibrium time was determined from kinetic data. A 50 mL Amount of adsorbed dye qe (mg/g) was determination by the
of varying concentration malachite green (10, 15, 25, 50, 100, and following equation:
150 mg/L) solution was added to 1 g of CLS in a Erlenmeyer flask (C0 − Ce ) V
and then mixed at 250 rpm for 60 min. The aqueous samples were qe = (1)
M
centrifuged (Hettich, Tuttlingen, Germany) at 4000 rpm for 1 min to
in which C0 and Ce are initial and equilibrium concentration of
remove the adsorbent. Dye concentration was measured via UV–vis
dye in liquid phase, respectively. V and M are solution volume
spectrophotometer GBC modelCintra-101 (Sydney, Australia) at
and adsorbent (g). Percentage of dye removing is obtained by the
617 nm. The adsorption of MG was studied after adding (0.1–1 g/L)
following equation:
of the adsorbent with size of adsorbent (mesh: 40, 60, 80, 120,
200), pH of solution (4–8), contact time (20, 30, 40, 50, 60 min) (C0 − Ce )
R% = × 100 (2)
and temperature (10–30 ◦ C). C0
C0 and Ce are initial and final dye concentration.
2.4. Optimization method (Taguchi design) Taguchi design was used in order to select the factors that
have influence on removal of dye. The dye removal percentage
Taguchi experimental design, which is developed by Taguchi, was selected as a response and experimental data were considered
is one of the most common ways to optimize adsorption param- as S/N ratio. With envisaging the characteristics, three S/N ratios
eters. In addition, simultaneous study of several parameters and exist; higher is better (HB), normal is best (NB) and lower is better
minimal number of experiments were achieved by this method. (LB) (Elizalde-González and García-Díaz, 2010; Engina et al., 2008;
S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89 85

Table 1 Table 2
parameter settings used in the experiments. Different parameter variables and their levels.

No. Factor L1 L2 L3 L4 L5 Expt. no. pH Temperature Adsorbent dosage Time Mesh

1 pH 4 5 6 7 8 1 1 1 5 3 1
2 Temperature 10 15 20 25 30 2 1 2 1 4 2
3 Adsorbent dosage 0.1 0.3 0.5 0.7 1 3 1 3 2 5 3
4 Time 20 30 40 50 60 4 1 4 3 1 4
5 Mesh 40 60 80 120 200 5 1 5 5 4 3
6 2 1 1 5 4
7 2 2 2 1 5
Wang et al., 2009). Since the high removal rate of dye is desired so 8 2 3 3 2 1
9 2 4 4 3 2
the larger is better was used. Response of this design depends on
10 2 5 5 3 1
the parameters and levels of experimental. Initially, we selected five 11 3 1 1 4 2
factors while they were potentially affecting the removal. Effective 12 3 2 2 5 3
parameters and considered parameters for every Taguchi design 13 3 3 3 1 4
are recorded in Table 1. Considering the mentioned factors and their 14 3 4 5 4 3
15 3 5 1 5 4
levels, 25 experiments have been designed (Table 2). 16 4 1 2 1 5
Obtained results were introduced to the software and the output 17 4 2 3 2 1
was evaluated an all Taguchi diagrams, longitudinal axis is related 18 4 3 4 3 2
to the investigating factors and transverse axis is related to S/N 19 4 4 5 3 1
20 4 5 1 4 2
proportion.
21 5 1 2 5 3
22 5 2 3 1 4
3.1. Effect of pH 23 5 3 5 4 3
24 5 4 1 5 4
25 5 5 2 1 5
As expected, pH is one of the most important parameters that
can affect adsorption process. The removal efficiency of dye was
examined in the pH range of 4.0 to 8.0 (Fig. 4a). Due to the malachite
green instability in pH of higher than 8, the effect of pH solution adsorptive process through dissociation of functional groups on
beyond 8 was not investigated. The results strongly verified that the active sites of the adsorbent. pH is, also, known to affect the
removal of dye from solution is influenced by pH, so the optimum structural stability of MG, and therefore, its color intensity.
pH is 5. This is likely because of adsorption process is affected by the
surface charge of adsorbent, the degree of ionization and speciation 3.2. Effect of temperature
of the adsorbent. The hydrogen ion and hydroxyl ions are adsorbed
quite strongly, and therefore, the adsorption of other ions is affected The influence of temperature on dye adsorption by CLS was
by the pH of the solution. And also the change of pH affects the studied (Fig. 4b). As seen, the percentage of dye adsorption

Fig. 4. (a) The effect of temperature on the removal of Malachite green by Cerastoderma lamarcki shell, initial Malachite green concentration = 20 mg/L, adsorbent dose = 1 g/L.
(b) The effect of adsorbent dose on the removal of Malachite green by Cerastoderma lamarcki shell, initial Malachite green concentration = 20 mg/L, adsorbent dose = 1 g/L. (c)
The effect of time on the removal of Malachite green by Cerastoderma lamarcki shell, initial Malachite green concentration = 20 mg/L, adsorbent dose = 1 g/L. (d) The effect of
particle size on the removal of Malachite green by Cerastoderma lamarcki shell, initial Malachite green concentration = 20 mg/L, adsorbent dose = 1 g/L. (e) The effect of pH on
the removal of Malachite green by Cerastoderma lamarcki shell, initial Malachite green concentration = 20 mg/L, adsorbent dose = 1 g/L.
86 S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89

increases sharp with the increasing temperature from 10 ◦ C to 160


10ppm
30 ◦ C. It can be assumed that, the phenomenon is an endothermic
process and has the most influence on the adsorption. Increasing 140 15ppm
the temperature, in fact the needed energy for the process is sup-
plied easier and increases the adsorption percentage. So 30 ◦ C was 120 20ppm

Concentraon(mg/L)
considered as the optimum temperature.
50ppm
100
3.3. Effect of adsorbent dose
100ppm
80
The effect of adsorbent dose in solution on the malachite green
150ppm
adsorption was investigated and the results are shown in Fig. 4c. As
60
seen, the percentage of MG removal increases with an increase in
adsorbent amount in solution. It means that increasing adsorbent
40
mass provides the more available pores and surface for adsorption.
Maximum removal occurs when amount of CLS is 1 g.
20

3.4. Time dependence of MG removal


0
0 50 100 150 200
Fig. 4d shows the time dependence of dye removal under opti-
mal experimental conditions. It was found that, under optimum me(min)
condition, the majority of MG was removed from the solution
Fig. 5. Contact times for the adsorptions of Malachite green onto Cerastoderma
after 60 min. It is clear that the removal of MG from the solu- lamarcki shell at various concentrations.
tion occurs very quickly. So the removal is almost completed after
approximately 60 min. The fast adsorption rate at the initial stage
Based on Eq. (3), a plot of Ce /qe versus Ce will result in a linear graph
is presumably related to an increased availability in the number of
with an intercept of 1/qmax KL and a slope of 1/qmax (Fig. 6a).
active binding sites on the adsorbent surface.

3.6.2. Freundlich isotherms


3.5. Effect of particle size
The Freundlich model proposes a multilayer sorption with a
heterogeneous system and describes reversible adsorption and is
As expected, size distribution is an important parameter and
not restricted to the formation of the monolayer. This isotherm
influences the rate of adsorption. So the effect of different par-
ticle sizes in the range of mesh of 60 to 120 on removal of MG
was investigated (Fig. 4e). It is interesting to note that an increase
in adsorbent from mesh of 60 to 120 improved the adsorption. A
possible reason for this behavior would be the existence of avail-
able surface for adsorption becomes more, thus, the percentage
of removal increases as the mesh increases. As the mesh size of
adsorbent increases from 120 to 200, the removal percent of dye
decreases. It may be contributed to the colloidal form of adsorbent
which led to a decrease in the adsorption of dye.

3.6. Adsorption equilibrium study

The experiments were taken to study the effect of contact time


varied from 10 to 165 min, for different initial dye concentration of
10, 15, 20, 50, 100 and 150 mg/L, in pH of 5 and CLS dosage of 1 g/L.
The nature of adsorbent and its available sorption sites affected the
time needed to reach the equilibrium. The relationship between
contact time and concentration of MG was studied and outlined
in Fig. 5. As seen, equilibrium contact time of CLS powder adsor-
bent has attained about 60 min. Thus equilibrium isotherms are
used to describe the experimental sorption data and the parameter
obtained from the different model:

3.6.1. Langmuir isotherms


According to the Langmuir isotherm theory, adsorption energy
is constant, independent of surface coverage and its equation
assumes that the surface is homogenous. The maximum adsorption
occurs when the surfaces are covered by a monolayer of adsorbate.
The linear Langmuir isotherm equation (3) is:
ce 1 ce
= + (3)
qe qmax KL qmax
where Ce is the equilibrium concentration of the MG (mg/L), qe is
Fig. 6. (a) The linear plots of Langmuir isotherm for the adsorptions of Malachite
adsorption capacity at equilibrium (mg/g), qmax is the maximum green onto Cerastoderma lamarcki shell. (b) The linear plots of Freundlich isotherm
adsorption capacity (mg/g) and KL is the Langmuir constant (L/mg). for the adsorptions of Malachite green onto Cerastoderma lamarcki shell.
S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89 87

Table 3
Isotherm constants for Malachite green onto Cerastoderma lamarcki shell.

Langmuir qmax (mg/g) KL (L/mg) R2


35.84 0.0039 0.7317
Freundlich nf KF R2
1.05 (mg/g)(L/g)1/n 0.9977
0.335

frequently used to describe the adsorption of inorganic and organic


compounds in solution. The linear form of Freundlich isotherm
equation (4) is:

1
ln qe = ln KF + ln Ce (4)
nF

where qe (mg/g) and Ce (mg/L) are the equilibrium concentration


of MG, onto the adsorbent and in solution, respectively. KF (mg/g)
(L/g)1/n is the Freundlich constant which is related to sorption
capacity and nF is the heterogeneity factor. Therefore, a plot of
ln qe versus ln Ce enables the constant KF and exponent 1/n to be
determined (Fig. 6b).
For modeling of equilibrium data, both Langmuir and Freundlich
isotherms were applied (Eqs. (3) and (4)). The Langmuir sorption
isotherm was analyzed by plotting Ce /qe versus Ce (Fig. 6a). And also
the applicability of Freundlich sorption isotherm was analyzed by
plotting ln (qe ) versus ln (Ce ) (Fig. 6b). The Langmuir and Freundlich
constants and related correlation coefficients are estimated.
In general, the values of n between 1 and 10 represent a favor-
able sorption and whereas (n < 1) demonstrates the adsorption
Fig. 7. (a) The linear plots of pseudo first-order model for the adsorptions of
process is chemical in nature. For the present study the value of Malachite green onto Cerastoderma lamarcki shell. (b) The linear plots of pseudo
n was greater than 1, revealing that adsorption was a favorable second-order model for the adsorptions of Malachite green onto Cerastoderma
process. lamarcki shell.
The comparison on the linear correlation coefficients of the
Langmuir and Freundlich isotherms for dye listed in Table 3. As
t and at equilibrium time, respectively. k1 and t are the first order
seen clearly, it could be concluded that the adsorption of MG onto
rate constant (min−1 ) and time (min).
CLS, best fitted to the Freundlich isotherm equation with R2 = 0.998
The log (qe − qt ) versus t was plotted and the values of qe and
rather than the Langmuir isotherm equation with R2 = 0.7317 under
k1 were determined from the intercept and slope of plot. The esti-
the temperature range studied.
mated values of k1 and qe are summarized in Table 4.
The pseudo-second-order equation is represented (Ho and
3.7. Adsorption kinetics McKay, 1999a, b) as:

One of the most important parameters that should be consid- t 1 t


= + (6)
ered for designing an adsorption system is predicting the rate of qt 2
k2 qe q e
reaction. Adsorption kinetic depends on the chemical and physical
properties of adsorbent which influence the adsorption mecha- where k2 is the equilibrium rate constant of pseudo-second order
nism. To elucidate the mechanisms of the sorption process, the equation (g/mg/min); k2 and qe are calculated from the plot of t/qe
experimental kinetic data were fitted by both pseudo-first-order versus t.
and pseudo-second-order models (Table 4). As expected, if the sorption follows pseudo second order model,
The pseudo-first-order equation is given as Lagergren equation plot of t/qt versus t will be linear and the qe and k2 can be calculated
(Lagergren, 1898; Ho, 2004): from the slope and intercept of the plot. Fig. 7 shows the linear plots
of the pseudo first order (a) and pseudo second-order (b) models
k1 t for the removal of MG by CLS. The estimated values of k2 and qe are
log (qe − qt ) = log qe − (5)
2.303 summarized in Table 4. Fig. 7 and also the correlation coefficient
which qt and qe (mg/g) the amounts are of adsorbed the concentra- value (R2 = 0.998) indicate that there is a good agreement between
tions of adsorbed dye pollutants per unit mass of adsorbent at time the kinetic data of adsorption and the pseudo second-order model.

Table 4
The calculated kinetic parameters for pseudo first-order and pseudo second-order models for the adsorptions of Malachite green onto Cerastoderma lamarcki shell.

C0 (mg/L) qexp (mg/g) Pseudo-first-order Pseudo-second-order


2
k1 (1/min) qc (mg/g) R k2 (g/mg min) qe (mg/g) R2

10 0.179465 0.059 0.388 0.9857 0.259 0.389 0.9961


15 0.282255 0.0 0.49 0.9937 0.177 0.585 0.9967
25 0.50176 0.049 0.863 0.9965 0.132 0.974 0.997
50 0.98991 0.053 2.03 0.9724 0.036 2.02 0.9925
100 2.156 0.056 3.93 0.9716 0.022 3.89 0.9944
150 3.54145 0.052 5.55 0.9898 0.158 5.7 0.995
88 S.Y. Kazemi et al. / Ecological Engineering 88 (2016) 82–89

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