Ultrasonics Sonochemistry 35 (2017) 112–123

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Design and construction of nanoscale material for ultrasonic assisted

adsorption of dyes: Application of derivative spectrophotometry and
experimental design methodology
Ahmad Reza Bagheri a, Mehrorang Ghaedi a,⇑, Arash Asfaram a, Ramin Jannesar b, Alireza Goudarzi c
a
Chemistry Department, Yasouj University, Yasouj 75918-74831, Iran
b
Department of Pathology, Yasuj University of Medical Sciences, Yasuj, Iran
c
Department of Polymer Engineering, Golestan University, Gorgan 49188-88369, Iran

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

Article history: Response surface methodology (RSM) based on central rotatable experimental design was used to inves-
Received 22 May 2016 tigate the effect of ultrasound assisted simultaneous adsorption process variables on Cu: ZnS-NPs-AC
Received in revised form 7 September 2016 from aqueous solution. Cu: ZnS-NPs-AC was characterized using field emission scanning electron micro-
Accepted 8 September 2016
scopy (FE-SEM), Energy Dispersive X-ray Spectroscopy (EDX) and X-ray diffraction (XRD). To overcome
Available online 13 September 2016
the severe methylene blue (MB) and brilliant green (BG) dyes spectral overlapping, derivative spec-
trophotometric method were successfully applied for the simultaneous determination of dyes in their
Keywords:
binary solutions. Simultaneous determination of the dyes can be carried out using the first-order and sec-
Brilliant green
Central composite design
ond order derivative signal at 664 and 663 nm for BG and MB, respectively. The factors investigated were
Cu: ZnS-NPs-AC pH (2.5–8.5), adsorbent mass (0.006–0.030 g), sonication time (1–5 min) and initial MB and BG concen-
Kinetics and isotherm study tration (3–15 mg L
1). Five levels, which were low level, center point, upper level and two axillar points,
Methylene blue were considered for each of the factors. The desirability function (DF: 0.9853) on the STATISTICA version
Ultrasonic assisted adsorption 10.0 software showed that the optimum removal (99.832 and 99.423% for MB and BG, respectively) was
obtained at pH 8.0, adsorbent mass 0.024 g, sonication time 4 min and 9 mg L
1 initial concentration for
each dye. Besides, the results show that obtained data were adequately fitted into the second-order poly-
nomial model, since the calculated model F value (172.96 and 96.35 for MB and BG, respectively) is
higher than the critical F value. The values of coefficient of determination (0.9968 and 0.9943 for MB
and BG, respectively) and adjusted coefficient of determination (0.9911 and 0.9840 for MB and BG,
respectively) are close to 1, indicating a high correlation between the observed and the predicted values.
The ultrasonic amplitude and adsorbent mass were found to be the most effective variable influencing
the adsorption process. The adsorption equilibrium was well described by the Langmuir isotherm model
with maximum adsorption capacity of 185.2 and 151.5 mg g
1 for MB and BG respectively on adsorbent.
The results indicate that pseudo-second-order kinetic equation and intra-particle diffusion model can
better describe the adsorption kinetics.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction largest category discharged by various industries such as textile,

Wastewater pollution is one of the big issues in environmental
conservation. Hospital wastewater carries several types of
contaminants, including heavy metals, biological oxygen demand,
chemical oxygen demand, color, and suspended solids [1–5].
Discharging colored effluents into aqueous environments such
as rivers and lakes can cause detrimental effects on aquatic life
[6,7]. Among various chromogenic substances, azo dyes are the
⇑ Corresponding author.
E-mail addresses: m_ghaedi@mail.yu.ac.ir, m_ghaedi@yahoo.com (M. Ghaedi).
food, paper, cosmetic, leather, and plastic [8,9].
Methylene blue (MB, C16H18N3SCl) as a thiazine cationic dye is
selected as a model organic (heterocyclic aromatic) compound
because it is known to adsorb more easily onto solids and in order
to evaluate the behavior of sorbent for the removal of organic
pollutants from its aqueous solutions [10,11]. MB has wider appli-
cations, which include textile, leather, pulp and paper, temporary
hair colorant, dyeing cottons, wools, coating for paper stock and
as analytical reagent [12–14].
Brilliant green (BG, C27H34N2O4S) is one of the commonly
known cationic dye used for various purposes, e.g. biological stain,

http://dx.doi.org/10.1016/j.ultsonch.2016.09.008
1350-4177/Ó 2016 Elsevier B.V. All rights reserved.
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123 113

dermatological agent, veterinary medicine, an additive to poultry explanation of the relationship between the response (MB and
feed to inhibit propagation of mold, intestinal parasites and fungus. BG dyes adsorption) and these independent parameters. Finally,
It is also extensively used in textile dying and paper printing Kinetic and equilibrium adsorption parameters were obtained
[15–17]. from the application of mathematical models to experimental data.
Moreover, MB and BG are often used as a probe molecules for
identifying the adsorption capacity of adsorbents [18,19]. There-
2. Experimental
fore, investigating the simultaneous removal of MB and BG from
wastewater are both practical and significant.
2.1. Materials and apparatus
For this purpose, many methods such as activated carbon
adsorption, chemical coagulation, ion exchange, electrolysis, bio-
Zinc acetate (Zn(CH3COO)2), thioacetamide (CH3CSNH2) were
logical treatments, etc have been developed [20–22]. Of these
purchased from Sigma Aldrich company. NaOH, HCl, EDTA, cupper
methods, Adsorption on solid surface is being growing interest in
acetate (Cu(CH3COO)2) and activated carbon were provided from
this field because of its lower price and activated Adsorption is
Merck (Darmstadt, Germany). All chemicals were used as received
highly effective for the removal of dyes and pigments as well as
without further purification. Cationic MB (analytical grade, C16H18-
other organic and inorganic pollution [23–25].
ClN3S, kmax: 664 nm) and BG (analytical grade, C27H34N2O4S, kmax:
Unfortunately, activated carbons due to difficultly for separa-
624 nm) supplied by Sigma Aldrich company were chosen as the
tion from solution and further discarding with process sludge
dye molecules for determining their adsorption on Cu: ZnS-NPs-
result in secondary pollution [26]. Nano scale material based
AC and were used without any purification. Dye solutions were
adsorbent show high surface area and reactive atom, large and
prepared by dissolving their appropriate amount in double dis-
wide dimension pores in addition to simple phase separation that
tilled water. The test solutions were prepared by diluting stock
candidate them as new strategy that enhance their application in
solution to the desired concentrations. Reverse osmosis Milli-Q
waste water treatment [27,28].
water (Millipore, Bedford, MA, USA) was used for all solutions
In recent years, various adsorbents have been applied for the
and dilutions.
removal of single component textile dyes [29,30]. However, indus-
A UV–visible spectrophotometer (model V-530, Jasco, Japan)
trial effluents contain more than one dye and little information is
equipped with a 1 cm quartz cell was used for recording the visible
available on multi-component dye adsorption [31]. On the other
spectra and absorbance measurements. A Metrohm 780 pH meter
hands, the simultaneous determination of dyes by the use of a tra-
(Metrohm Co., Herisau, Switzerland) was used for monitoring the
ditional spectrophotometric method is difficult because of a seri-
pH values. A Tecno GAZ SPA Ultra Sonic System (Parma, Italy)
ous overlapping of their absorption spectra [32,33]. Derivative
ultrasound cleaner bath was used at 130 W at 40 kHz frequency
spectrophotometry is an analytical technique of great utility for
with maximum about 3 L of water throughout the experiment.
resolving mixtures with overlapping spectra [34]. The fundamental
The apparatuses have accurate digital time controller and thermo-
principles of derivative spectrophotometry have been described by
statically controlled heater.
Talsky et al. [35]. In this paper, we simultaneously analyze MB and
The morphologies of the adsorbent were characterized by using
BG using first and second order derivatives, respectively.
a field emission scanning electron microscope (FE-SEM, Hitachi S-
Ultrasonic-assisted adsorption is a competitor and popular
4160, Japan). The X-ray diffraction (XRD, Philips PW 1800) was
technique due to its advantages over other conventional tech-
produced using a sealed tube and the wavelength of X-ray was
niques [36]. This method has been increasingly used for the
0.154 nm (Cu K-alpha, 40 kV and 40 mA) at angles ranging from
adsorption of target compounds from wastewater [37].
20 to 70°. Energy dispersive X-ray spectroscopy (EDX, Oxford INCA
Ultrasonic-assisted exhibits many substantial improvements in
II energy solid state detector) was coupled with SEM to examine
adsorption process, as it requires much lower amount of adsorbent,
surface elemental composition and obtain surface elemental distri-
reduces adsorption time and increases adsorption efficiency
bution maps.
[31,38].
This phenomenon is due to the fact that ultrasound irradiation
and its secondary effect, cavitation (nucleation, growth and tran- 2.2. Statistical analysis
sient collapse of tiny gas bubbles) improve the mass transfer
through convection pathway [39]. Additionally, this is emerged The experimental results of the central composite design (CCD)
from physical phenomena such as micro-streaming, micro- were analyzed using STATISTICA 10.0 software (State-Ease Inc.,
turbulence, acoustic (or shock) waves and micro jets without sig- Minneapolis, USA) and the optimal conditions were determined
nificant change in equilibrium characteristics of the adsorption/ to obtain maximum adsorption. The experimental data were ana-
desorption system [40]. lyzed with a second order polynomial model validated by statisti-
RSM is an empiric statistical technique that uses quantitative cal analysis. Mean values were considered significantly different
data found from suitable designed tests to determine operating when p < 0.05. The derivative spectra were generated using the
conditions and regression model [41]. RSM is helpful in the indi- software Origin (State Software Inc., Origin Lab, Version 9.0) from
vidual and interaction effects of independent variables and opti- Savitzky–Golay procedure [43], applying the smoothing function
mizing the process parameters with limited number of (15 points).
experiments [42].
In this study, a novel adsorbent has been applied in the adsorp- 2.3. Synthesis of copper-doped zinc sulfide nanoparticles loaded on
tion of different dyes. Methylene blue (MB) and brilliant green activated carbon (Cu: ZnS-NPs-AC)
(BG), as a typical cationic dyes, were selected as the main adsor-
bates for the present study. The central composite Design (CCD) The fabrication of copper-doped zinc sulfide nanoparticles
of the RSM was employed to investigate the effects of significant loaded on activated carbon (Cu: ZnS-NPs-AC) was carried out as
operating parameters including pH, adsorbent mass, sonication follows: 6 mL of 1 mol L
1 zinc acetate solution was mixed with
time and initial MB and BG concentration on ultrasound assisted 0.003 mmol EDTA solution and 15 mL of 0.4 mol L
1 thioacetamide
dyes adsorption and to find the most suitable combination of vari- solution at pH of 6.0, then deionized water was added to the mixed
ables resulting in maximum dyes adsorption. The second-order solutions to make a total volume of 100 mL. In the following,
polynomial equations (regression models) provided an excellent 100 mL of the prepared solution in a baker was transferred to
114 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123
Microwave oven with power of 180 W for 30 min. After 30 min the
baker containing the reaction solution along with the prepared
nanoparticles in bottom of the baker was removed from Micro-
wave oven.
The obtained ZnS nanoparticles were filtered and washed sev-
eral times by deionized water and then dried at room temperature.
In the next step, 0.3 g of the prepared nanoparticles was dispersed
into 50 mL deionized water to form an insoluble suspension, then
1.4 mL of 0.02 mol L
1 cupper acetate solution was added to the
suspension to form the Cu: ZnS nanoparticles. Finally, the homoge-
nous deposition of the Cu: ZnS-NPs on activated carbon (AC) was
carried out by adding 15 g of AC to the prepared Cu: ZnS-NPs sus-
pension along with strong stirring for 17 h at room temperature.
The prepared Cu: ZnS-NPs-AC was then filtered, washed several
times by de-ionized water, dried at 50 °C and used as an absorbent
for adsorptions experiments.
2.4. The simultaneous analysis in binary solutions
Fig. 1a shows the zero order spectra of MB, BG containing
9 mg L
1 of dyes and their binary mixture. The maximum wave-
lengths (kmax) appear at 664 and 624 nm for MB and BG, respec-
tively. Because of the spectral overlapping of the zero-order
spectra, simultaneous determination of both dyes in binary solu-
tions is not accurate by direct absorption measurements. There-
fore, derivative spectrophotometric method was applied for the
simultaneous determination of each individual dye in the presence
of the other.
The first-and second order derivative absorption spectra of dyes
in single and binary solutions are given in Fig. 1b and c. According
to the first derivative spectra, the BG could be determined at
644 nm, where the first-order derivative spectrum of MB was zero
(Fig. 1b); as at 663 nm the second-order derivative spectrum of BG
was equal to zero, this wavelength could be selected for MB
(Fig. 1c).
Fig. 1. (a) Zero-order absorption spectra at wavelengths of 300–800 nm for both dyes in single and binary system, (b) First and (c) second order derivative spectra of BG and
MB in single and binary solutions and (d) calibration curve (1–10 mg L
1) of the first and second order derivative spectrophotometry for both dyes in binary system.
The calibration equations (Fig. 1d) for the two dyes were con-
structed by plotting the absolute values of the first-order (DA/
Dk) and second order (D2A/D2k) derivative signal at 664 and
663 nm for BG and MB, respectively, against different concentra-
tions (1–10 mg L
1) of the two dyes. The concentration of each
dye could be calculated from the calibration graphs.
2.5. Ultrasound assisted batch adsorption experiments
Adsorption experiments were carried out in batch mode to
investigate the effect of experimental factors (pH, adsorbent mass,
sonication time and initial MB and BG concentration) on the
ultrasound assisted simultaneous adsorption of dyes on Cu:
ZnS-NPs-AC. The effect of experimental factors such as pH
(2.5–8.5), adsorbent mass (0.006–0.030 g), sonication time
(1–15 min), MB and BG dye concentration (3–15 mg L
1) at
constant temperature, was investigated employing one response
surface methodology approach.
The adsorption experiments were carried out in the presence of
ultrasound to study the effect of different parameters on the effi-
ciency of adsorption. A optimum set of experimental conditions,
Cu: ZnS-NPs-AC mass (0.024 g) was added to 50 mL of aqueous
binary dyes solution of known dyes concentration (9 mg L
1 for
each dye) at pH (8.0) of the solution was adjusted using NaOH
and/or HCl. The experiments were performed at room temperature
(25 °C) and predetermined 4.0 min sonication time in ultrasonic
bath. The adsorbent was separated from solution by centrifugation
at 3000 rpm for 3 min and subsequently the absorption of MB and
BG solution was recorded by UV–Vis spectrophotometer. Finally,
their concentration was calculated based on calibration curve
obtained by first and second-order derivative spectrum. The binary
dye adsorption efficiency and the equilibrium adsorption capacity,
(qe (mg g
1)) of each dye were calculated using Eqs. (1) and (2):


C0;i
Ct;i
R% ¼  100% ð1Þ
C0;i
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123 115


ðC0;i
Ct;i ÞV
qe ¼
W
where C0,i and Ct,i is the initial and final concentration (mg L
1) of
dyes (i) in binary system, Ct,i is the concentration of each dye at
equilibrium time, V is the volume of solution (50 mL); W is the
weight of the dry Cu: ZnS-NPs-AC.
2.6. Adsorption isotherms
Ultrasound assisted adsorption isotherm studies were con-
ducted the adsorption system (MB and BG dyes solution and Cu:
ZnS-NPs-AC) at optimum conditions (initial MB and BG dyes con-
centration: 3–25 mg L
1, pH of 8.0, adsorbent mass: 0.006–
0.024 g, sonication time of 4 min at 25 °C) in the presence of ultra-
sound. After the system approached equilibrium time, the mixture
was centrifuged to separate the supernatant and spent adsorbent.
Finally, their concentration was calculated based on calibration
curve obtained by first and second-order derivative spectrum. Sev-
eral adsorption isotherm (Langmuir, Freundlich, Temkin and
Dubinin-Radushkevich models (Table 1) were used to analyze the
experimental equilibrium data of dyes adsorption.
2.7. Adsorption kinetics modeling
Ultrasound assisted batch kinetic biosorption studies were con-
ducted in an ultrasonic bath at a predetermined time interval ran-
ged from 1 to 5 min using 50 mL of dyes solution pH of 8.0 and a
fixed adsorbent mass of 0.024 g. Afterwards, all samples were cen-
trifuged for 3 min at 3000 rpm and the concentration of each dye
was calculated based on calibration curve obtained by derivative
spectrum. The dynamics of dyes adsorption onto Cu: ZnS-NPs-AC
were analyzed using four different kinetic models: the pseudo-
first-order, pseudo-second-order, intraparticle diffusion and Elo-
vich models (Table 1).
2.8. Experimental design and statistical analyzes
ð2Þ
The RSM method is based on the fit of mathematical models
(linear, square polynomial functions and others) to the experimen-
tal results generated from the designed experiment and the verifi-
cation of the model obtained by means of statistical techniques.
RSM is used to determine the optimum conditions, for the ultra-
sound assisted adsorption of dyes [41]. A central composite rotat-
able experimental design (CCRD) for five independent variables
was used. The independent variables selected for the optimization
were pH, adsorbent mass (g), sonication time (min) and initial MB
and BG concentration (mg L
1) and designated as X1–X5, respec-
tively. Regression analysis was performed on the data obtained
from the experiments.
The lowest low, center point, high and highest levels of each
variable were coded as
a,
1, 0, +1 and +a respectively (Table 2).
A five-level-five-factor design was applied, which produced 32
experimental runs, which comprises of 16 full factorial points, 10
axial points and 6 center-axial points. In order to correlate the
response variable to the independent variables, multiple regres-
sions were used to fit the coefficient of the second-order polyno-
mial model of the response. The quality of the fit of the model
was evaluated using a test of significance and analysis of variance
(ANOVA).
The correlation between response and the selected factors can
been expressed by a quadratic equation that is given as [10,31]:
Xk Xk Xk
1 Xk
Y ¼ b0 þ bX
i¼1 i i
þ b XX
i¼1 ii i i
þ i¼1
b XX
j¼iþ1 ij i j
ð3Þ
where Y is the predicted response (predicted adsorption), Xi, Xj are
the independent variables in coded levels, bi the linear coefficient;
bii the squared coefficient; and bij the cross-product coefficient, k
is the number of factors (independent variables), and e is the model
error. The quality of fit of the polynomial model equation was
expressed by the coefficient of determination (R2) and adjusted
R2. The model F-value (Fisher variation ratio), probability value

Table 1
Isotherm and kinetic models.

Isotherm/ Equation Plot Nomenclature Ref.

kinetic models
Isotherm Langmuir Ce
¼ Q m1kL þ QCme Ce/qe vs. Where Ce denotes the equilibrium MB or BG concentration in mg L
1, qe represents the [7]
qe
Ce equilibrium adsorption capacity of adsorbent in mg g
1, Qm is the maximum adsorption
capacity at saturation of the monolayer coverage (mg g
1), KL is the Langmuir equilibrium
adsorption constant (L mg
1) related to the free energy of adsorption
RL ¼ 1þðK1L C 0 Þ – Where C0 is the initial concentration of dye (mg L
1). The value of RL indicates the type of [48]
isotherm to be irreversible (RL = 0), favorable (0 < RL < 1), linear (RL = 1) or unfavorable
(RL > 1)
Freundlich lnqe ¼ lnK F þ 1n lnC e ln qe vs. Where KF (L mg
1) is the Freundlich constant and n is the intensity of adsorption. The value [13]
ln Ce of n is an indication of the favorability of adsorption. Values of n > 1 represent favorable
nature of adsorption
Temkin qe ¼ B1 lnK T þ B1 lnC e qe vs. ln Where B1 = RT/b, b is the Temkin constant related to heat of sorption (J mol
1), KT is the [16]
Ce equilibrium binding constant (L g
1), R the gas constant (8.314 J mol
1 K
1) and T is the
absolute temperature (K)
Dubinin- lnqe ¼ lnQ s
ke2 ln qe vs. Where QS is the maximum adsorption capacity (mg g
1), k is the activity coefficient related [49]
Radushkevich e2 to adsorption mean free energy (mol2 J2) and e is the Polanyi potential
e ¼ RTlnð1 þ Ce Þ
1 –
E ¼ p1ffiffiffiffi
2k
– The E value gives information about adsorption mechanism, and more specifically its [50]
physical (E < 8 kJ mol
1) or chemical (between 8 and 16 kJ mol
1) nature
Kinetic Pseudo-first- lnðqe
qt Þ ¼ ln qe
k1 t ln Where qe and qt (mg g
1) are the adsorption amounts at equilibrium and in time, [51]
order kinetic (qe
qt) respectively, k1 is the pseudo-first-order rate constant (min
1) and k2 is the pseudo-second
vs. t order rate constant (g mg
1 min
1)
Pseudo- t
qt ¼ k 1q2 þ qt t/qt vs. t [52]
2 e e
second-order
kinetic
Intraparticle qt ¼ kdiff t1=2 þ C qt vs. t1/2 where kdiff (mg g
1 min
1/2) is intraparticle diffusion rate constant with C as intercept along [53]
diffusion qt axis
Elovich qt ¼ 1
b lnðtÞ þ 1
b lnð abÞ qt vs. ln t Where a is the initial sorption rate constant (mg g
1 min
1), and the parameter b is related to [54]
the extent of surface coverage and activation energy for chemisorption (g mg
1)
116 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123

Table 2
Experimental design in term of coded factors and results of the central composite design for the ultrasound assisted adsorption of dyes.

Coded Factors Levels

a Low (
1) Central (0) High (+1) +a
X1 pH 2.500 4.000 5.500 7.000 8.500
X2 Adsorbent mass (g) 0.006 0.012 0.018 0.024 0.030
X3 Sonication time (min) 1.000 2.000 3.000 4.000 5.000
X4 MB concentration (mg L
1) 3.000 6.000 9.000 12.00 15.00
X5 BG concentration (mg L
1) 3.000 6.000 9.000 12.00 15.00
Factors R% MB R% BG
a b c a b c
Run X1 X2 X3 X4 X5 Exp. Pred. Res. Exp. Pred. Res.
1
1
1
1
1 +1 75.000 74.117 0.883 66.000 65.896 0.104
2 +1
1
1
1
1 81.200 80.970 0.230 77.320 77.181 0.139
3
1 +1
1
1
1 81.300 81.338
0.038 72.550 73.215
0.665
4 +1 +1
1
1 +1 97.300 97.411
0.111 89.000 89.021
0.021
5
1
1 +1
1
1 99.400 98.932 0.468 81.200 81.131 0.069
6 +1
1 +1
1 +1 90.550 90.155 0.395 83.800 83.087 0.713
7
1 +1 +1
1 +1 99.800 99.673 0.127 91.260 91.352
0.092
8 +1 +1 +1
1
1 99.300 99.826
0.526 99.686 99.742
0.056
9
1
1
1 +1
1 70.000 69.462 0.538 69.900 69.846 0.054
10 +1
1
1 +1 +1 65.300 64.835 0.465 79.200 78.502 0.698
11
1 +1
1 +1 +1 90.000 89.803 0.197 73.300 73.406
0.106
12 +1 +1
1 +1
1 96.000 96.456
0.456 74.400 74.471
0.071
13
1
1 +1 +1 +1 72.430 71.727 0.703 86.800 86.172 0.628
14 +1
1 +1 +1
1 83.400 83.350 0.050 89.880 89.217 0.663
15
1 +1 +1 +1
1 95.700 95.918
0.218 88.100 88.241
0.141
16 +1 +1 +1 +1 +1 94.300 94.591
0.291 90.900 90.397 0.503
17
a 0 0 0 0 88.020 89.048
1.028 81.200 80.823 0.377
18 +a 0 0 0 0 96.128 95.704 0.424 92.931 93.913
0.982
19 0
a 0 0 0 63.102 64.666
1.564 77.299 78.531
1.232
20 0 +a 0 0 0 95.994 95.033 0.961 91.361 90.734 0.627
21 0 0
a 0 0 72.483 73.035
0.552 66.600 66.364 0.236
22 0 0 +a 0 0 92.928 92.980
0.052 92.473 93.314
0.841
23 0 0 0
a 0 99.240 99.652
0.412 80.846 80.639 0.207
24 0 0 0 +a 0 85.392 85.583
0.191 77.234 78.046
0.812
25 0 0 0 0
a 95.205 94.927 0.278 85.543 85.237 0.305
26 0 0 0 0 +a 88.060 88.942
0.882 85.525 86.436
0.910
27 (C) 0 0 0 0 0 92.000 92.643
0.643 89.305 89.300 0.005
28 (C) 0 0 0 0 0 92.730 92.643 0.087 88.000 89.300
1.300
29 (C) 0 0 0 0 0 93.200 92.643 0.557 88.800 89.300
0.500
30 (C) 0 0 0 0 0 93.600 92.643 0.957 90.200 89.300 0.900
31 (C) 0 0 0 0 0 92.630 92.643
0.013 90.500 89.300 1.200
32 (C) 0 0 0 0 0 92.300 92.643
0.343 89.600 89.300 0.300

(C): Center point.

a
Experimental values of response.
b
Predicted values of response by RSM proposed model.
c
Residual.

(Prob > F), and adequate precision (AP) were the main indicators
demonstrating the significance and adequacy of the used model.
3. Results and discussion
3.1. Characterization of Cu: ZnS-NPs-AC
The size and surface morphology of the prepared Cu:
ZnS-NPs-AC were investigated by FE-SEM (Fig. 2a, b) showed
a homogenous distribution of the nano-size spherical form
particles with the approximate diameter less than 20 nm.
Fig. 3a, b shows the EDX spectrum of the prepared sample.
According to the obtained EDX analysis, the chemical composi-
tion of the prepared sample is Cu0.2 ZnS0.9. The observed Au
peaks in the EDX spectrum are corresponded to the signal
detected from the gold coating by sputtering during FE-SEM
sample preparation. The EDS spectra of the AC and formed
Cu: ZnS-NPs-AC is presented in Fig. 3a, b in order to investigate
their localized elemental information. Zn, S and Cu are the
dominant elements throughout the surface of the nanoparticles
with weight percentages of 68.20, 30.00 and 1.80%, respectively.
From EDX analysis of Cu: ZnS-NPs-AC was also found that, the
weight percentage ratios of C: Zn: S: Cu content in the
adsorbent after loaded on activated carbon are 97.3: 1.6: 0.8:
0.4% respectively.
Fig. 3c shows the obtained XRD pattern of the prepared Cu:
ZnS-NPs. The four observed XRD peaks at 2h = 28.5, 40.4, 48.3
and 57.2° were attributed to the (0 0 2), (1 0 2), (1 1 0) and
(1 1 2) lattice planes of the wurtzite (hexagonal) structure of
ZnS, respectively (JCPDS, No. 00-036-1450). In addition, the
three observed XRD peaks at 2h = 29.5, 48.3 and 57.2° were
attributed to the (1 0 2), (1 1 0) and (2 0 2) lattice planes of
the hexagonal (Covellite) structure of CuS, respectively (JCPDS,
No. 00-006-0464).
3.2. Optimization of the procedure
3.2.1. The model fitting and statistical analysis
The analysis of variance (ANOVA) for ultrasound assisted
adsorption study of MB and BG dyes was applied in order to ensure
a desirable model. The ANOVA results are shown in Table 3. Below
are empirical polynomial quadratic model Eqs. (4) and (5) for MB
and BG respectively that were used to fit the data:
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123
Fig. 2. FE-SEM of (a) Cu: ZnS-NPs and (b) Cu: ZnS-NPs-AC.
Y ðR%MBÞ ¼
30:5 þ 2:9X 1 þ 18541X 2 þ 397X 3
1:0X 4
0:4X 5
þ 114:4X 1 X 2
1:0X 1 X 3
310:2X 2 X 3 þ 185:1X 2 X 4
þ 138:3X 2 X 5
0:6X 3 X 4
04X 3 X 5
0:2X 4 X 5

88840X 22
2:4X 23
Y ðR%BGÞ ¼
630:4 þ 102X 1 þ 21931X 2 þ 258X 3 þ 82X 4
09X 1 X 3

03X 1 X 4 þ 1191X 2 X 3
1502X 2 X 4 þ 424X 2 X 5
04X 3 X 5

0:21X 21
324124X 22
24X 23
03X 24
01X 25
where (X1), (X2), (X3), (X4) and (X5) are the pH, adsorbent mass, son-
ication time and initial MB and BG concentration respectively, as
the experimental variables. The negative coefficients for the model
components indicate the unfavorable effects on the dye percentage
removal. While, the positive coefficients indicate favorable effects
on the dyes percentages removal. The significance of each model
parameter will be determined by the statistical analysis.
According to ANOVA results (Table 3), the model F-values with
a very low probability value (p < 0.0001) were determined as
172.96 and 96.35 for MB and BG, respectively, indicating that both
models were significant.
The non-significance of lack-of-fit is favorable and it specifies
the high predictability of the model. The ‘‘Lack of Fit F-value” of
4.365 and 1.595 for MB and BG, respectively implies the Lack of
Fit is not significant relative to the pure error. There is a 6.362
and 31.25% for MB and BG, respectively chance that a ‘‘Lack of Fit
F-value” with this magnitude could occur due to noise.
The correctness and goodness of the models were checked
by the coefficient of determination values. The R2 values of full
117
ð4Þ
Fig. 3. (a) EDX of (a) Cu: ZnS-NPs and (b) Cu: ZnS-NPs-AC and (c) XRD pattern of Cu:
ZnS-NPs-AC.
ð5Þ
second-order polynomial regression models were found as
0.968 (adj. 0.9911) and 0.9943 (adj. 0.9840) for MB and BG
respectively. Diagnostic plots, such as the predicted versus
actual values (Fig. 4a), help determine the model satisfactori-
ness. These plots show an adequate agreement between real
data and the ones gained from the models. Hence, all predic-
tive models can be used to navigate the design space defined
by the CCD.
The coefficient of variance (CV), as the ratio of the standard
error of the estimate to the mean value of the observed response
(as a percentage), identifies the reproducibility of the model. A
model typically can be considered reproducible if its CV is not
>10% [44] According to Table 3, the CV values obtained for both
responses studied are relatively small with none of them exceeding
1.50%. The statistical results obtained, show that the above models
adequately predicted adsorption of MB and BG within the range of
variables studied.
‘‘Adequate Precision (AP)’’ measures the signal to noise ratio. A
ratio >4 is desirable [45]. Here the ratio of 44.14 and 39.52 for MB
and BG indicates an adequate signal.
118 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123

Table 3
Analysis of variance (ANOVA) table for response surface quadratic model.

Source of variation Dfa R% MB R% BG Regression coefficients

b c
SS MS F-value P-value SS MS F-value P-value R% MB R% BG
Model 20 3343.92 167.20 172.96 <0.0001 2153.65 107.68 96.35 <0.0001
3.47
63.36
X1 1 66.45 66.45 68.74 <0.0001 257.01 257.01 229.97 <0.0001 2.94 10.21
X2 1 1383.25 1383.25 1430.92 <0.0001 223.38 223.38 199.88 <0.0001 1854.10 2193.13
X3 1 596.71 596.71 617.27 <0.0001 1089.47 1089.47 974.82 <0.0001 39.65 25.84
X4 1 296.92 296.92 307.16 <0.0001 10.09 10.09 9.03 0.0120
0.95 8.16
X5 1 53.73 53.73 55.58 <0.0001 2.15 2.15 1.93 0.1926
0.39
2.05
X1X2 1 16.97 16.97 17.56 0.0015 0.38 0.38 0.34 0.5700 114.44 17.19
X1X3 1 33.87 33.87 35.04 0.0001 28.26 28.26 25.29 0.0004
0.97
0.89
X1X4 1 0.25 0.25 0.25 0.6246 31.69 31.69 28.35 0.0002
0.03
0.31
X1X5 1 0.67 0.67 0.70 0.4220 1.00 1.00 0.89 0.3650
0.05
0.06
X2X3 1 55.43 55.43 57.34 <0.0001 8.17 8.17 7.31 0.0205
310.21 119.12
X2X4 1 177.69 177.69 183.81 <0.0001 116.94 116.94 104.64 <0.0001 185.14
150.19
X2X5 1 99.10 99.10 102.52 <0.0001 9.34 9.34 8.36 0.0145 138.26 42.44
X3X4 1 55.20 55.20 57.11 <0.0001 3.81 3.81 3.41 0.0920
0.62 0.16
X3X5 1 24.55 24.55 25.40 0.0004 23.61 23.61 21.13 0.0008
0.41
0.40
X4X5 1 37.58 37.58 38.87 <0.0001 4.64 4.64 4.15 0.0664
0.17 0.06
X21 1 0.13 0.13 0.14 0.7200 6.84 6.84 6.12 0.0309
0.03
0.21
X22 1 300.04 300.04 310.38 <0.0001 39.94 39.94 35.74 <0.0001
88839.97
32412.44
X23 1 170.21 170.21 176.08 <0.0001 164.11 164.11 146.84 <0.0001
2.41
2.37
X24 1 0.0005 0.0005 0.0005 0.9729 181.77 181.77 162.64 <0.0001
0.01
0.28
X25 1 0.92 0.92 0.95 0.3501 21.99 21.99 19.68 0.0010
0.02
0.10
Residual 11 10.63 0.97 12.29 1.12
Lack of Fit 6 8.93 1.49 4.37 0.0636 8.07 1.35 1.59 0.3125
Pure Error 5 1.70 0.34 4.22 0.84
Cor Total 31 3354.56 2165.94
Model Summary Statistics
Response Standard Deviation (SD) Coefficient of Variance (C.V.%) R2 Adj-R2 Pred-R2 Adequate precision (AP)
44.14 39.52
R% MB 0.983 1.114 0.9968 0.9911 0.9295 44.14
R% BG 1.057 1.262 0.9943 0.9840 0.8997 39.52
a
Degree of freedom.
b
Sum of Square.
c
Mean of Square.

Plot of percentage dye removal versus residual (Fig. 4b) indi-
cated the outliers if any, all other points were found to fall in the
range of +1.5 to
1.5. Fig. 4c shows the normal probability plots
of the studentized residuals for copper removal efficiency. It is
clear from the figure that the residuals follow a normal distribu-
tion, in which the points follow a straight line. The results can be
shown in Fig. 4d with the help of a histogram. Histograms of the
residuals show the distribution of the residuals for all observations.
The figure shows a symmetrical histogram.
3.2.2. Analysis of the response surface
The interaction between two factors and their optimum levels
can be easily understood and located using response surface plot.
Figs. 5 and 6 show the 3D response surfaces and the corresponding
contour plots as the functions of two variables at the center level of
other variables, respectively. The nonlinear nature of all 3D
response surfaces and the respective contour plots demonstrated
that there were considerable interactions between each of the
independent variables and the MB and BG removal efficiency.
The removal percentage has a positive and similar trend with
adsorbent dosage and higher removal percentage at higher adsor-
bent mass is attributed to its high specific surface area and small
particle size (Fig. 5a). With lower amounts of adsorbent, due to
the possible saturation of reaction sites, a significant decrease in
the removal percentage was observed. On the other hand, maxi-
mum MB adsorption could occur at a sonication time of above
4 min showing the rapidity and high efficiency of the adsorbent.
The initial fast adsorption is attributed to the increase in available
surface area and vacant site following the efficient dispersion of
adsorbent into the solution by ultrasonic power.
Fig. 5b shows the 3D surface plot for R% MB of interaction
between initial MB concentration and adsorbent mass. The maxi-
mum percentage uptake of MB dye was observed when initial
MB concentration was at minimum point, while adsorbent mass
was at maximum point within the studied range. As the initial
MB concentration increased, the percentage uptake decreased.
Decrease in percentage uptake at high initial MB concentration
might be due to insufficient of available binding sites and increase
in the ratio of the MB cationic dye to the amount of the adsorbent.
The combined effect of pH and sonication time for adsorption on
BG removal is shown in the 3D plot of Fig. 6a. It was observed that
percentage BG removal increased with increasing the sonication
time and pH increased. This means that higher values of dye
removal could be obtained by simultaneous increase in sonication
time and initial solution pH. As pH decreased, the % removal of BG
(cationic dye) decreased suggested repulsion between positive
charge dye molecule and adsorbent at low pH. As pH of the solu-
tion increased, the adsorbent surface negative charge would
increase and as a result electrostatic attraction of the dye molecule
increased.
The effects of MB concentration and sonication time on the
removal percentages of BG are shown in Fig. 6b. It was observed
that the removal percentage of BG dye decreases upon increasing
the MB concentration, which is due to the decrease in the ratio
of available surface adsorption sites to the dyes molecules.
3.2.3. Optimization of CCD by desirability function (DF) for ultrasonic
assisted adsorption of dyes
Maximum adsorption efficiency for MB and BG dyes by Cu:
ZnS-NPs-AC and the corresponding optimal experimental condi-
tions of the independent variables were determined by using the
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123
Fig. 4. (a) Comparison between observed and predicted values of response variables, (b) residual versus observed values. After, (c) the normal probability plot of the residuals
and histogram of Raw Residuals for adsorption of dyes.
desirability function (DF) [34] on the STATISTIA (Fig. 7) and
confirmed by further experimental work. The optimum conditions
with DF of 0.9853 were found to be pH 8.0, adsorbent mass
(0.024 g), sonication time (4 min) and initial MB and BG
concentration (9 mg L
1) giving a maximum MB and BG removal
of 99.832 and 99.423% respectively. The optimum conditions were
checked experimentally by running five experiments under the
same conditions at 25 °C. The results showed an average MB and
BG adsorption efficiency of 99.200 ± 0.701% and 98.45 ± 1.120%.
There was a high degree of agreement between the replicate
experimental results and predicted optimum results indicating
that the central composite design could be used effectively for
the evaluation and optimization of the effects of the adsorption
independent variables on the removal efficiency of MB and BG dyes
from aqueous solution using Cu: ZnS-NPs-AC.
3.3. Adsorption isotherms
The adsorption equilibrium information is the most important
part of information in understanding an adsorption process. The
equilibrium experimental data for the adsorption of the tested
dyes on Cu: ZnS-NPs-AC was compared using four isotherm equa-
tions namely, Langmuir, Freundlich, Temkin and Dubinin-
Radushkevich. The adsorption isotherm parameters obtained from
the linear regression (Table 1) analysis of Ce/qe versus Ce data for
Langmuir model, ln qe versus ln Ce data for Freundlich model, ln
119
qe versus e2 data for Dubinin-Radushkevich and qe versus ln Ce
data for Temkin model are given in Table 4 together with their cor-
responding regression coefficients (R2).
The experimental data of both dyes produced a higher value of
correlation coefficients (0.993) with Langmuir model than Fre-
undlich (0.922–0.980) in all of the adsorbent values studied, indi-
cating the acceptability of the model of homogeneous sorption
phenomena for the Cu: ZnS-NPs-AC-dyes system.
The predicted Qm from the Langmuir model at 0.006 g adsor-
bent are 185.2 and 151.5 mg g
1 for MB and BG respectively, while
at 0.024 g the value decreased to 36.60 and 43.30 mg g
1 for MB
and BG respectively, which could be due to the mass of the adsor-
bent particle that lead to an increase in amount of adsorbent at
higher Cu: ZnS-NPs-AC. The RL values of the Langmuir isotherm
for all the adsorbent dosages are between 0 and 1, which indicated
that the adsorption process between dyes and Cu: ZnS-NPs-AC are
favorable. It is clear from Table 4 that the values of the Freundlich
exponents, n, were greater than n > 1 represents a favorable
adsorption condition.
The free energy of dyes biosorption was considered via
Dubinin-Radushkevich model. As can be seen from Table 4, the
experimental results were fitted by Dubinin-Radushkevich model
with a relatively good correlation coefficient (0.913–0.979). The
values of the calculated mean energy (E) of biosorption for both
dyes were less than 8 kJ mol
1, indicating that the adsorption pro-
cess of dyes was probably controlled as physically [46].
120 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123

Fig. 6. Response surfaces plots of BG adsorption onto the Cu: ZnS-NPs-AC

Fig. 5. Response surface plots for combined effect of (a) sonication time and
adsorbent mass and (b) MB concentration and adsorbent mass on adsorption
efficiency of MB dye.
The results were also fitted by the Temkin model (Table 4),
which suggested a reduction in the heat of biosorption along with
coverage due to adsorbent-adsorbate interactions [47]. As a result,
adsorption of dyes could be characterized by a uniform distribu-
tion of binding energies up to maximum value.
adsorbent: (a) the effects of sonication time and pH and (b) the effects of the
sonication time and MB concentration.
Table. 5 shows the comparison of the maximum monolayer
adsorption capacities of various adsorbents for dyes. The values
of Qm in this study (MB = 185.2 and BG = 151.5 mg g
1) is larger
than those in most of the previous studies. The results show that
Cu: ZnS-NPs-AC are effective for MB and BG dyes and can be used
as a substitute for commercially nanomaterial adsorbent. The
reduction in time compared to conventional adsorption is due to

Fig. 7. Desirability function profile for ultrasound assisted adsorption of MB and BG dyes.
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123 121

Table 4
Model constant parameters and correlation coefficients calculated for the ultrasound assisted adsorption of dyes onto Cu: ZnS-NPs-AC. (pH = 8.0, C0 = 3–18 mg L
1, sonication
time = 4 min, V = 50 mL, adsorbent mass = 0.006–0.024 g and T = 25 °C).

Response R% MB R% BG
Adsorbent mass (g) 0.006 g 0.012 g 0.024 g 0.006 g 0.012 g 0.024 g
Isotherm Parameters Value of parameters
Langmuir Qm (mg.g
1) 185.2 72.50 36.60 151.5 67.10 43.30
KL (L mg
1) 0.410 0.800 1.800 0.985 1.500 2.380
RL 0.120–0.448 0.0650–0.300 0.030–0.156 0.053–0.253 0.018–0.036 0.0230–0.123
R2 0.998 0.997 0.998 0.997 0.993 0.996
Freundlich n 1.430 1.869 2.726 1.872 2.209 2.563
KF (L mg
1) 5.500 4.300 3.700 6.200 4.700 4.140
R2 0.954 0.980 0.944 0.978 0.922 0.980
Temkin B1 36.12 15.46 6.830 32.27 13.85 7.910
KT(L mg
1) 5.015 8.482 26.20 10.54 17.25 37.74
R2 0.979 0.987 0.997 0.993 0.988 0.988
Dubinin-Radushkevich QS (mg g
1) 97.82 47.12 29.63 102.0 52.59 32.57
K  10
8 10.00 8.000 5.000 7.000 6.000 3.000
E (kJ mol
1) 2.236 2.500 3.162 2.673 2.887 4.082
R2 0.913 0.913 0.961 0.935 0.979 0.913

Table 5
Comparison for the adsorption of dyes by different methods and adsorbents.

Adsorbent Method Dye Qmax (mg g
1) Contact time (min) Ref.
Ag nanoparticles loaded on activated carbon Magnetic stirrer MB 34.50 10.0 [55]
Palladium nanoparticles loaded on activated carbon Magnetic stirrer MB 33.20 9.50 [55]
Ruthenium nanoparticles loaded on activated carbon Magnetic stirrer MB 185.2 27.0 [56]
Zinc oxide nanorods loaded on activated carbon Magnetic stirrer MB 75.76 20.0 [57]
Fe3O4/reduced graphene oxide Heterogeneous Fenton degradation MB – 60.0 [58]
Co doped Ti/TiO2 nanotube/PbO2 anodes Electrocatalytic degradation MB – 120 [59]
Boron doped diamond grown on Ti substrates Degradation using BDD/Ti electrodes BG – 300 [60]
Saccharomyces cerevisiae Biosorption BG 18.80 5.00 [61]
Zn doped SnO2 nanoparticles Photocatalytic degradation BG – 105 [62]
Activated carbon (AC) Ultrasound-assisted BG 47.10 3.00 [63]
Mn-doped Fe3O4-NP-AC Ultrasound-assisted BG 87.57 3.00 [63]
Rice husk ash Magnetic stirrer BG 26.19 300 [64]
NaOH treated saw dust Magnetic stirrer BG 58.48 180 [65]
Ruthenium nanoparticles loaded on activated carbon Magnetic stirrer BG 94.70 45.0 [66]
Cu: ZnS-NPs-AC Magnetic stirrer MB 89.32 4.00 This study
Cu: ZnS-NPs-AC Ultrasonic assisted MB 185.2 4.00
Cu: ZnS-NPs-AC Magnetic stirrer BG 69.33 4.00
Cu: ZnS-NPs-AC Ultrasonic assisted BG 151.5 4.00

Table 6
Estimated parameters of the kinetic models for the ultrasound assisted adsorption of dyes onto Cu: ZnS-NPs-AC. (pH = 8.0, C0 = 3–9 mg L
1, sonication time = 0–7 min, V = 50 mL,
adsorbent mass = 0.024 g and T = 25 °C).

Response R% MB R% BG
Concentration (mg L
1) 3 mg L
1 6 mg L
1 9 mg L
1 3 mg L
1 6 mg L
1 9 mg L
1
Model Parameters Value of parameters
First-order-kinetic k1 (min
1) 0.394 0.443 0.350 0.313 0.430 0.286
qe (calc) (mg g
1) 3.280 9.050 13.57 3.241 7.435 9.010
R2 0.958 0.921 0.963 0.973 0.987 0.978
Pseudo-second-order-kinetic k2 (min
1) 0.183 0.070 0.037 0.142 0.080 0.049
qe (calc) (mg g
1) 12.85 24.94 47.20 13.00 24.81 36.77
R2 0.999 0.998 0.997 0.998 0.999 0.996
Intraparticle diffusion Kdiff (mg g
1 min
1/2) 1.068 2.600 4.745 1.282 2.303 3.574
C (mg g
1) 9.366 16.35 31.22 8.713 17.22 24.76
R2 0.997 0.994 0.978 0.983 0.998 0.974
Elovich b (g mg
1) 0.960 0.400 0.220 0.801 0.448 0.290
a (mg g
1 min
1) 17,011 3564 9160 2738 5000 9430
R2 0.929 0.933 0.929 0.901 0.948 0.915
Experimental data qe (exp) (mg g
1) 12.23 23.28 44.22 12.23 23.38 34.78
122 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123
the cavitational effect. The rapid uptake and quick establishment of
equilibrium shows the efficiency of ultrasound power in wastewa-
ter treatment. Ultrasound is a highly recommended tool to
improve the mass transfer process and the affinity between dyes
and adsorbent.
3.4. Adsorption kinetics
The kinetics of biosorption is an important characteristic in
evaluating the efficiency of sorption process. Several kinetic
models are available to understand the behavior of the adsorbent
and also to examine the controlling mechanism of the adsorption
process. In this study mostly used models, pseudo-first order,
pseudo-second order, Elovich and intraparticle diffusion models
have been tested for the simultaneous ultrasound assisted adsorp-
tion of dyes onto the Cu: ZnS-NPs-AC. The calculated kinetic
parameters obtained from the pseudo first- and second- order,
intraparticle diffusion and elovich equations are listed in Table 6.
Results showed high correlation coefficient values (>0.996) for
both systems and a good agreement between calculated (qe,cal)
and experimental qe (qe,exp) values indicating the applicability of
the pseudo-second order kinetic model for MB and BG- Cu: ZnS-
NPs-AC systems. Adsorption of MB and BG dyes (3 mg L
1) onto
Cu: ZnS-NPs-AC showed higher k2 values than other concentra-
tions, suggested the rate of adsorption on Cu: ZnS-NPs-AC was high
and required less time to reach equilibrium point.
From the figures obtained from the intraparticle diffusion, the
straight line did not pass through the origin and this indicated that
the intraparticle diffusion was not only the rate-controlling step.
The result showed that the adsorption process was complex and
involved more than one mechanism. The calculated parameters
were tabulated in Table 1. The R2 value was between 0.9738 and
0.9965. Generally, it could be stated that the adsorption process
tended to follow intraparticle diffusion. For the Elovich equation,
the regression coefficients are in the range of 0.9005 to 0.9475. This
means that the fitting of experimental kinetics data to the Elovich
model is not good.
4. Conclusion
The main goal of this study was to evaluate the performance of
copper-doped zinc sulfide nanoparticles loaded on activated car-
bon (Cu: ZnS-NPs-AC) adsorbent for the ultrasound assisted
adsorption of MB and BG cationic dyes from aqueous solution.
Derivative spectrophotometry was used for simultaneous determi-
nation of the dyes, and the response surface methodology (RSM)
was applied to analyze the adsorption behavior of the two dyes
onto adsorbent.
The first and second order derivative spectra showed that BG
and MB can be determined at 664 and 663 nm, respectively. Statis-
tical analysis was carried out in order to find out the optimal pro-
cess parameters for increased dyes uptake by Cu: ZnS-NPs-AC. The
CCD shows that the initial dyes concentration has a negative effect
on the adsorption efficiency (responses) of dyes, whereas sonica-
tion time, adsorbent mass and pH have positive effects on the
response. The proposed quadratic model obtained by CCD agreed
well with the experimental data with good correlation coefficients
(R2 > 0.990). Kinetic studies suggest that the equilibrium is
achieved within only 5 min and the pseudo-second-order model
is followed. The adsorption isotherms could be well fitted by the
Langmuir adsorption isotherm equation based on the maximum
monolayer biosorption capacity for MB and BG is 185.2 and
151.5 mg g
1, respectively. The results indicated that Cu: ZnS-
NPs-AC could be a potential alternative adsorbent for the simulta-
neous removal of dyes from aqueous solution.
Acknowledgments
The authors are grateful to Yasouj University, Iran for the finan-
cial support of this work and also sincerely appreciate the signifi-
cant contributions made by the Dena pathobiology laboratory
(Yasouj, Iran).
References
[1] I. Anastopoulos, I. Massas, C. Ehaliotis, Use of residues and by-products of the
olive-oil production chain for the removal of pollutants from environmental
media: a review of batch biosorption approaches, J. Environ. Sci. Health. Part A
50 (2015) 677–718.
[2] M.K. Maruthamuthu, S.P. Nadarajan, I. Ganesh, S. Ravikumar, H. Yun, I.K. Yoo, S.
H. Hong, Construction of a high efficiency copper adsorption bacterial system
via peptide display and its application on copper dye polluted wastewater,
Bioprocess Biosys. Eng. 38 (2015) 2077–2084.
[3] A.K. Ojha, V.K. Bulasara, Adsorption characteristics of jackfruit leaf powder for
the removal of Amido black 10B dye, Environ. Prog. Sustainable Energy 34
(2015) 461–470.
[4] S. Louaer, Y. Wang, L. Guo, Fast synthesis and size control of gibbsite
nanoplatelets, their pseudomorphic dehydroxylation, and efficient dye
adsorption, ACS Appl. Mater. Interface 5 (2013) 9648–9655.
[5] A. Asfaram, M. Ghaedi, G.R. Ghezelbash, Biosorption of Zn2+, Ni2+ and Co2+ from
water samples onto Yarrowia lipolytica ISF7 using a response surface
methodology, and analyzed by inductively coupled plasma optical emission
spectrometry (ICP-OES), RSC Adv. 6 (2016) 23599–23610.
[6] Y. Chen, S.R. Zhai, N. Liu, Y. Song, Q.D. An, X.W. Song, Dye removal of activated
carbons prepared from NaOH-pretreated rice husks by low-temperature
solution-processed carbonization and H3PO4 activation, Bioresour. Technol.
144 (2013) 401–409.
[7] C.K. Lim, H.H. Bay, C.H. Neoh, A. Aris, Z. Abdul Majid, Z. Ibrahim, Application of
zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7:
isotherm, kinetic and thermodynamic studies, Environ. Sci. Poll. Res. Int. 20
(2013) 7243–7255.
[8] N. Daneshvar, A.R. Khataee, Removal of azo dye C.I. acid red 14 from
contaminated water using Fenton, UV/H2O2, UV/H2O2/Fe(II), UV/H2O2/Fe
(III) and UV/H2O2/Fe(III)/oxalate processes: a comparative study, J. Environ.
Sci. Health Part A 41 (2006) 315–328.
[9] T.D. Pham, M. Kobayashi, Y. Adachi, Adsorption characteristics of anionic azo
dye onto large a-alumina beads, Colloid Poly. Sci. 293 (2015) 1877–1886.
[10] A. Asfaram, M. Ghaedi, M.H.A. Azqhandi, A. Goudarzi, M. Dastkhoon, Statistical
experimental design, least squares-support vector machine (LS-SVM) and
artificial neural network (ANN) methods for modeling the facilitated
adsorption of methylene blue dye, RSC Adv. 6 (2016) 40502–40516.
[11] K. Mukherjee, A. Kedia, K. Jagajjanani Rao, S. Dhir, S. Paria, Adsorption
enhancement of methylene blue dye at kaolinite clay-water interface
influenced by electrolyte solutions, RSC Adv. 5 (2015) 30654–30659.
[12] T. Liu, Y. Li, Q. Du, J. Sun, Y. Jiao, G. Yang, Z. Wang, Y. Xia, W. Zhang, K. Wang,
Adsorption of methylene blue from aqueous solution by graphene, Colloids
Surf. B 90 (2012) 197–203.
[13] T. Maneerung, J. Liew, Y. Dai, S. Kawi, C. Chong, C.H. Wang, Activated carbon
derived from carbon residue from biomass gasification and its application for
dye adsorption: kinetics, isotherms and thermodynamic studies, Bioresour.
Technol. 200 (2016) 350–359.
[14] X. Sun, T. Kurokawa, M. Suzuki, M. Takagi, Y. Kawase, Removal of cationic dye
methylene blue by zero-valent iron: effects of pH and dissolved oxygen on
removal mechanisms, J. Environ. Sci. Health Part A 50 (2015) 1057–1071.
[15] E. Alipanahpour Dil, M. Ghaedi, A. Asfaram, A. Goudarzi, Synthesis and
characterization of ZnO-nanorods loaded onto activated carbon and its
application for efficient solid phase extraction and determination of BG from
water samples by micro-volume spectrophotometry, New J. Chem. 39 (2015)
9407–9414.
[16] H.I. Chieng, N. Priyantha, L.B.L. Lim, Effective adsorption of toxic brilliant green
from aqueous solution using peat of Brunei Darussalam: isotherms,
thermodynamics, kinetics and regeneration studies, RSC Adv. 5 (2015)
34603–34615.
[17] R. Kumar, M.O. Ansari, M. Barakat, Adsorption of brilliant green by surfactant
doped polyaniline/MWCNTs composite: evaluation of the kinetic,
thermodynamic, and isotherm, Ind. Eng. Chem. Res. 53 (2014) 7167–7175.
[18] M. Jamshidi, M. Ghaedi, K. Dashtian, A.M. Ghaedi, S. Hajati, A. Goudarzi, E.
Alipanahpour, Highly efficient simultaneous ultrasonic assisted adsorption of
brilliant green and eosin B onto ZnS nanoparticles loa ded activated carbon:
artificial neural network modeling and central composite design optimization,
Spectrochim. Acta Part A 153 (2016) 257–267.
[19] S. Agarwal, I. Tyagi, V.K. Gupta, A.R. Bagheri, M. Ghaedi, A. Asfaram, S. Hajati, A.
A. Bazrafshan, Rapid adsorption of ternary dye pollutants onto copper (I) oxide
nanoparticle loaded on activated carbon: experimental optimization via
response surface methodology, J. Environ. Chem. Eng. 4 (2016) 1769–1779.
[20] L. Labiadh, M.A. Oturan, M. Panizza, N.B. Hamadi, S. Ammar, Complete removal
of AHPS synthetic dye from water using new electro-fenton oxidation
catalyzed by natural pyrite as heterogeneous catalyst, J. Hazard. Mater. 297
(2015) 34–41.
 A.R. Bagheri et al. / Ultrasonics Sonochemistry 35 (2017) 112–123
[21] S. Mosleh, M.R. Rahimi, M. Ghaedi, K. Dashtian, Sonophotocatalytic
degradation of trypan blue and vesuvine dyes in the presence of blue light
active photocatalyst of Ag3PO4/Bi2S3-HKUST-1-MOF: central composite
optimization and synergistic effect study, Ultrason. Sonochem. 32 (2016)
387–397.
[22] J. Vidal, L. Villegas, J.M. Peralta-Hernandez, R. Salazar Gonzalez, Removal of
Acid Black 194 dye from water by electrocoagulation with aluminum anode, J.
Environ. Sci. Health Part A 51 (2016) 289–296.
[23] A. Asfaram, M. Ghaedi, S. Hajati, M. Rezaeinejad, A. Goudarzi, M.K. Purkait,
Rapid removal of Auramine-O and Methylene blue by ZnS: Cu nanoparticles
loaded on activated carbon: a response surface methodology approach, J.
Taiwan Inst. Chem. Eng. 53 (2015) 80–91.
[24] S. Salimpour Abkenar, R.M. Malek, F. Mazaheri, Dye adsorption of cotton fabric
grafted with PPI dendrimers: isotherm and kinetic studies, J. Environ. Manage.
163 (2015) 53–61.
[25] E. Kacan, Optimum BET surface areas for activated carbon produced from
textile sewage sludges and its application as dye removal, J. Environ. Manage.
166 (2016) 116–123.
[26] F.M. Machado, C.P. Bergmann, T.H. Fernandes, E.C. Lima, B. Royer, T. Calvete, S.
B. Fagan, Adsorption of Reactive Red M-2BE dye from water solutions by
multi-walled carbon nanotubes and activated carbon, J. Hazard. Mater. 192
(2011) 1122–1131.
[27] H. Mazaheri, M. Ghaedi, A. Asfaram, S. Hajati, Performance of CuS nanoparticle
loaded on activated carbon in the adsorption of methylene blue and
bromophenol blue dyes in binary aqueous solutions: using ultrasound
power and optimization by central composite design, J. Mol. Liq. 219 (2016)
667–676.
[28] E.A. Dil, M. Ghaedi, A.M. Ghaedi, A. Asfaram, A. Goudarzi, S. Hajati, M. Soylak, S.
Agarwal, V.K. Gupta, Modeling of quaternary dyes adsorption onto ZnO–NR–
AC artificial neural network: analysis by derivative spectrophotometry, J. Ind.
Eng. Chem. 34 (2016) 186–197.
[29] E.A. Dil, M. Ghaedi, A. Ghaedi, A. Asfaram, M. Jamshidi, M.K. Purkait,
Application of artificial neural network and response surface methodology
for the removal of crystal violet by zinc oxide nanorods loaded on activate
carbon: kinetics and equilibrium study, J. Taiwan Inst. Chem. Eng. 59 (2016)
210–220.
[30] M. Ghaedi, P. Ghobadzadeh, S.N. Kokhdan, M. Soylak, Oxidized multiwalled
carbon nanotubes as adsorbents for kinetic and equilibrium study of removal
of 5-(4-dimethyl amino benzylidene) rhodanine, Arabian J. Sci. Eng. 38 (2013)
1691–1699.
[31] A. Asfaram, M. Ghaedi, S. Hajati, A. Goudarzi, Synthesis of magnetic c-Fe2O3-
based nanomaterial for ultrasonic assisted dyes adsorption: modeling and
optimization, Ultrason. Sonochem. 32 (2016) 418–431.
[32] J. Zolgharnein, M. Bagtash, T. Shariatmanesh, Simultaneous removal of binary
mixture of Brilliant Green and Crystal Violet using derivative
spectrophotometric determination, multivariate optimization and adsorption
characterization of dyes on surfactant modified nano-c-alumina, Spectrochim.
Acta Part A 137 (2015) 1016–1028.
[33] E. Alipanahpour Dil, M. Ghaedi, A. Asfaram, Optimization and modeling of
preconcentration and determination of dyes based on ultrasound assisted-
dispersive liquid–liquid microextraction coupled with derivative
spectrophotometry, Ultrason. Sonochem. 34 (2017) 27–36.
[34] F. Ansari, M. Ghaedi, M. Taghdiri, A. Asfaram, Application of ZnO nanorods
loaded on activated carbon for ultrasonic assisted dyes removal: experimental
design and derivative spectrophotometry method, Ultrason. Sonochem. 33
(2016) 197–209.
[35] G. Talsky, L. Mayring, H. Kreuzer, High-resolution, higher-order UV/VIS
derivative spectrophotometry, Angew. Chem. 17 (1978) 785–799.
[36] F.N. Azad, M. Ghaedi, K. Dashtian, S. Hajati, V. Pezeshkpour, Ultrasonically
assisted hydrothermal synthesis of activated carbon–HKUST-1-MOF hybrid for
efficient simultaneous ultrasound-assisted removal of ternary organic dyes
and antibacterial investigation: Taguchi optimization, Ultrason. Sonochem. 31
(2016) 383–393.
[37] A. Asfaram, M. Ghaedi, A. Goudarzi, Optimization of ultrasound-assisted
dispersive solid-phase microextraction based on nanoparticles followed by
spectrophotometry for the simultaneous determination of dyes using
experimental design, Ultrason. Sonochem. 32 (2016) 407–417.
[38] A. Asfaram, M. Ghaedi, F. Yousefi, M. Dastkhoon, Experimental design and
modeling of ultrasound assisted simultaneous adsorption of cationic dyes onto
ZnS: Mn-NPs-AC from binary mixture, Ultrason. Sonochem. 33 (2016) 77–89.
[39] O. Acisli, A. Khataee, S. Karaca, M. Sheydaei, Modification of nanosized natural
montmorillonite for ultrasound-enhanced adsorption of Acid Red 17, Ultrason.
Sonochem. 31 (2016) 116–121.
[40] S. Khanjani, A. Morsali, Ultrasound-promoted coating of MOF-5 on silk fiber
and study of adsorptive removal and recovery of hazardous anionic dye ‘‘congo
red”, Ultrason. Sonochem. 21 (2014) 1424–1429.
[41] F.N. Azad, M. Ghaedi, A. Asfaram, A. Jamshidi, G. Hassani, A. Goudarzi, M.H.A.
Azqhandi, A. Ghaedi, Optimization of the process parameters for the
adsorption of ternary dyes by Ni doped FeO(OH)-NWs-AC using response
surface methodology and an artificial neural network, RSC Adv. 6 (2016)
19768–19779.
[42] Z. Zhang, H. Zheng, Optimization for decolorization of azo dye acid green 20 by
ultrasound and H2O2 using response surface methodology, J. Hazard. Mater.
172 (2009) 1388–1393.
123
[43] A. Savitzky, M.J. Golay, Smoothing and differentiation of data by simplified
least squares procedures, Anal. Chem. 36 (1964) 1627–1639.
[44] A. Asfaram, M. Ghaedi, A. Goudarzi, M. Rajabi, Response surface methodology
approach for optimization of simultaneous dye and metal ion ultrasound-
assisted adsorption onto Mn doped Fe3O4-NPs loaded on AC: kinetic and
isothermal studies, Dalton Trans. 44 (2015) 14707–14723.
[45] A. Asfaram, M. Ghaedi, S. Hajati, A. Goudarzi, Ternary dye adsorption onto
MnO2 nanoparticle-loaded activated carbon: derivative spectrophotometry
and modeling, RSC Adv. 5 (2015) 72300–72320.
[46] M. Ghaedi, Z. Rozkhoosh, A. Asfaram, B. Mirtamizdoust, Z. Mahmoudi, A.A.
Bazrafshan, Comparative studies on removal of Erythrosine using ZnS and
AgOH nanoparticles loaded on activated carbon as adsorbents: kinetic and
isotherm studies of adsorption, Spectrochim. Acta Part A 138 (2015) 176–186.
[47] M. Dastkhoon, M. Ghaedi, A. Asfaram, A. Goudarzi, S.M. Langroodi, I. Tyagi, S.
Agarwal, V.K. Gupta, Ultrasound assisted adsorption of malachite green dye
onto ZnS:Cu-NP-AC: equilibrium isotherms and kinetic studies – response
surface optimization, Sep. Purif. Technol. 156 (2015) 780–788.
[48] I.A. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye on high-surface-
area activated carbon prepared from coconut husk: equilibrium, kinetic and
thermodynamic studies, J. Hazard. Mater. 154 (2008) 337–346.
[49] M. Dubinin, V. Serpinsky, Isotherm equation for water vapor adsorption by
microporous carbonaceous adsorbents, Carbon 19 (1981) 402–403.
[50] H.I. Chieng, L.B. Lim, N. Priyantha, Enhancing adsorption capacity of toxic
malachite green dye through chemically modified breadnut peel: equilibrium,
thermodynamics, kinetics and regeneration studies, Environ. Technol. 36
(2015) 86–97.
[51] Y. Wong, Y. Szeto, W. Cheung, G. McKay, Pseudo-first-order kinetic studies of
the sorption of acid dyes onto chitosan, J. Appl. Poly. Sci. 92 (2004) 1633–1645.
[52] Y.-S. Ho, Review of second-order models for adsorption systems, J. Hazard.
Mater. 136 (2006) 681–689.
[53] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J. Sanit.
Eng. Div. 89 (1963) 31–60.
[54] O. Aksakal, H. Ucun, Equilibrium, kinetic and thermodynamic studies of the
biosorption of textile dye (Reactive Red 195) onto Pinus sylvestris L, J. Hazard.
Mater. 181 (2010) 666–672.
[55] M. Ghaedi, S. Heidarpour, S. Nasiri Kokhdan, R. Sahraie, A. Daneshfar, B.
Brazesh, Comparison of silver and palladium nanoparticles loaded on activated
carbon for efficient removal of Methylene blue: kinetic and isotherm study of
removal process, Powder Technol. 228 (2012) 18–25.
[56] H. Mazaheri, M. Ghaedi, S. Hajati, K. Dashtian, M.K. Purkait, Simultaneous
removal of methylene blue and Pb2+ ions using ruthenium nanoparticle-
loaded activated carbon: response surface methodology, RSC Adv. 5 (2015)
83427–83435.
[57] M. Ghaedi, A.G. Nasab, S. Khodadoust, R. Sahraei, A. Daneshfar,
Characterization of zinc oxide nanorods loaded on activated carbon as cheap
and efficient adsorbent for removal of methylene blue, J. Ind. Eng. Chem. 21
(2015) 986–993.
[58] B. Yang, Z. Tian, L. Zhang, Y. Guo, S. Yan, Enhanced heterogeneous Fenton
degradation of Methylene Blue by nanoscale zero valent iron (nZVI) assembled
on magnetic Fe3O4/reduced graphene oxide, J. Water Process Eng. 5 (2015)
101–111.
[59] C. Wang, F. Wang, M. Xu, C. Zhu, W. Fang, Y. Wei, Electrocatalytic degradation
of methylene blue on Co doped Ti/TiO2 nanotube/PbO2 anodes prepared by
pulse electrodeposition, J. Electroanal. Chem. 759 (2015) 158–166.
[60] F.L. Migliorini, J.R. Steter, R.S. Rocha, M.R.V. Lanza, M.R. Baldan, N.G. Ferreira,
Efficiency study and mechanistic aspects in the Brilliant Green dye
degradation using BDD/Ti electrodes, Diamond Related Mater. 65 (2016) 5–12.
[61] M. Ghaedi, S. Hajati, B. Barazesh, F. Karimi, G. Ghezelbash, Saccharomyces
cerevisiae for the biosorption of basic dyes from binary component systems
and the high order derivative spectrophotometric method for simultaneous
analysis of Brilliant green and Methylene blue, J. Ind. Eng. Chem. 19 (2013)
227–233.
[62] N. Shanmugam, T. Sathya, G. Viruthagiri, C. Kalyanasundaram, R. Gobi, S.
Ragupathy, Photocatalytic degradation of brilliant green using undoped and Zn
doped SnO2 nanoparticles under sunlight irradiation, Appl. Surf. Sci. 360
(2016) 283–290.
[63] A. Asfaram, M. Ghaedi, S. Hajati, A. Goudarzi, E.A. Dil, Screening and
optimization of highly effective ultrasound-assisted simultaneous adsorption
of cationic dyes onto Mn-doped Fe3O4-nanoparticle-loaded activated carbon,
Ultrason. Sonochem. 34 (2017) 1–12.
[64] V.S. Mane, I. Deo, Mall, V. Chandra Srivastava, Kinetic and equilibrium
isotherm studies for the adsorptive removal of Brilliant Green dye from
aqueous solution by rice husk ash, J. Environ. Manage. 84 (2007) 390–400.
[65] V.S. Mane, P.V. Babu, Studies on the adsorption of Brilliant Green dye from
aqueous solution onto low-cost NaOH treated saw dust, Desalination 273
(2011) 321–329.
[66] S. Hajati, M. Ghaedi, B. Barazesh, F. Karimi, R. Sahraei, A. Daneshfar, A. Asghari,
Application of high order derivative spectrophotometry to resolve the spectra
overlap between BG and MB for the simultaneous determination of them:
ruthenium nanoparticle loaded activated carbon as adsorbent, J. Ind. Eng.
Chem. 20 (2014) 2421–2427.