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 Page 1 of 38 Dalton Transactions
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DOI: 10.1039/C5DT01504A

1 Response surface methodology approach for optimization of simultaneous

2 dyes and metal ions ultrasound-assisted adsorption onto Mn doped Fe3O4-NPs
loaded on AC: Kinetic and isotherm study
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5 Arash Asfaram a, Mehrorang Ghaedi *a, Alireza Goudarzi b, Maryam Rajabi c

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7 Chemistry Department, Yasouj University, Yasouj 75918-74831, Iran.
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8 Department of Polymer Engineering, Golestan University, Gorgan, 49188-88369, Iran
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9 Chemistry Department, Faculty of Science, Semnan University, Semnan 35195-363, Iran
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* Corresponding author at: Tel.: +98 741 2223048; fax: +98 741 2223048.
E-mail address: [email protected]; [email protected] (M. Ghaedi)

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42 Abstract
43 In the present work, the usefulness of ultrasonic power as dispersion and mixing tool to
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44 accelerate the adsorption of Safranin O (SO), Methylene blue (MB), Pb2+ ions and Cr3+ ions onto
45 novel composite of Fe3O4-NPs-AC as adsorbent was investigated. This new material extensively

Dalton Transactions Accepted Manuscript

46 were characterized and analyzed by different techniques such as XRD, FESEM, Raman
47 spectroscopy and FT-IR. The Central Composite Design (CCD) based on designed runs reveal
48 that adsorbent mass, sonication time, MB concentration, SO concentration, Pb2+ ions and Cr3+
49 ions concentration and some of their interactions have significant contribution on the target
50 compounds removal percentages. The combination of response surface methodology and
51 Design-Expert software used to qualify and estimates the influence and magnitude of each term
52 contribution on response. The optimization over following investigated interval of effective
53 variables, adsorbent mass (0.01-0.03 g), sonication time (2-6 min), initial dyes concentration (5-
54 25 mg L-1), initial metal ions concentration (20-60 mg L-1) reveal that fixing the experimental
55 variables at 0.025 g of Mn-Fe3O4-NPs-AC, 3 min sonication time, 20 mg L-1 of MB, 10 mg L-1
56 of SO, 38 mg L-1 of Pb2+ ions and 42 mg L-1 of Cr3+ ions at room temperature lead to
57 achievement of best characteristics performance. Conduction of 32 experiments according to
58 limitation of CCD and their subsequent analysis of variance (ANOVA) gives useful information
59 about significant and also approximate contribution of each term (main and interaction of
60 variables) in empirical equation on expected response. The results indicate that the R2 values are
61 more than 0.988 and adjusted R2 are in a reasonable agreement with R2. Under the optimal
62 conditions, the MB, SO, Pb2+ ions and Cr3+ ions removal efficiency reached 99.54%, 98.87%,
63 80.25% and 99.54% after 3 min, while their equilibrium data with high performance can be
64 represented with Langmuir isotherm and a pseudo second-order kinetic model. The maximum
65 adsorption capacity in single component system, 229.4 mg g-1 for MB, 159.7 mg g-1 for SO,
66 139.5 mg g-1 for Pb2+ ions and 267.4 mg g-1 for Cr3+ ions support high efficiency of Mn-Fe3O4-
67 NPs-AC as new adsorbent.
68
69 Keywords: Adsorption, Dyes, Heavy metals, Mn-Fe3O4-NPs-AC, Nanoparticles, Response
70 surface methodology, Ultrasound-assisted removal.
71 .
72

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73 1. Introduction
74 Environmental pollution as greatest ecosystem problem seriously damage the human health and
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75 other organism life forms.1 Main attention and hazards are devoted to the presence of dyes and
76 heavy metals that subsequently generate very serious environmental problems. These expected

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77 limitations and hazards is concerned to their toxic effects, non-biodegradability, accumulation in
78 living tissues which possible their simple arrival to the human and animal bodies through food
79 consumption.2-4
80 Lead source including battery, mining, lead smelting, metal plating, paper and pulp,
81 metallurgical finishing and metal processing into the environment.5 Cr3+ ions act as useful and
82 essential element for humans, while its high content is toxic.6, 7
Chromium is utilized in
83 industries like electroplating, leather tanning, metal finishing, and nuclear power plant and textile
84 and chromate preparation manufacturers. Chromium is considerably carcinogenic and causes
85 problems such as chromosomal abnormality and bioaccumulation into flora and fauna.8, 9 Dye
86 present in wastewater come from textile, leather, paper, and plastics consume, while methylene
87 blue (MB; Fig. 1, thiazine cationic dye) has extensive application in industry, biology and
88 chemistry.10, 11
89 Safranin-O (SO, reddish brown powder, Fig. 1) also is a cationic (azine) dye belong to synthetic
90 dyes12 with high dissolubility in water and extensively applied in food products for flavoring and
91 coloring candies and cookies in addition to tannin, cotton, fibers, wool, silk, leather and paper
92 coloring and treatment.13
93 All above mention hazards related to dyes and understudy metal ions encourage the researchers
94 to design and develop novel method for their efficient and quantitative removal by a simple, low
95 cost and fast procedure. A method that applicable for their simultaneous efficient removal in
96 short time with low consumption of reagents is highly recommended.
97 These wide application make emphasis on researchers to efficiently conduct process for removal
98 of SO and MB. The more common treatment techniques that have been used to reduce the
99 heavy-metal and dyes content in wastewaters to permissible concentrations include adsorption,
100 biosorption,14-16 chemical precipitation,17 electrokinetic coagulation,18 reverse osmosis,19 ion
101 exchange,20 filtration and membrane,21 ozonation,22 fungal decolorization,23 and adsorption 24-32

102 processes.

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103 Among them, adsorption based on their unique offer-mentioned properties has talent to be as
104 best promising technologies for environment cleaning from heavy metals and dyes.33, 34
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105 Combination of unique properties of adsorption with distinct ability and prominent properties of
106 nano-scale materials cause achievement of simultaneous adsorption and removal of dyes and

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107 pollutants. These protocols can be accomplished with application of mathematical models to
108 relevance and evaluate the statistical significance of factors and their interaction29, 35-37
that
109 permits development of low cost and short time clean up systems. Multivariate designs
110 composed of different stages such as responses analysis (qualitative or quantitative) and lateral
111 estimation and express of its dependency to factors (sole and interaction) using at least
112 experiments.
113 This procedure is superior to one way classification and optimization in term of requirement of
114 large number of experiments and serious time reduction, while impossible to exactly give idea
115 about variables interactions.38 These problems simply can be resolved with at least possible
116 number of experiments namely response surface methodology (RSM) in different branches. 36
117 The purpose of this study was to investigate the adsorption characteristics of dyes and heavy
118 metal ions by Mn doped Fe3O4-NPs loaded on AC. The effects of experimental parameters such
119 as adsorbent mass, sonication time and initial concentration of target compounds on their
120 adsorption were analyzed using RSM. The isotherm and kinetic parameters were also evaluated
121 using the adsorption measurements. The maximum capacity (Qmax) of adsorbent was comparable
122 to other adsorbents.
123
124 2. Experimental
125 2.1. Instruments and reagents
126 Ammonium iron (III) sulfate (NH4 Fe (SO4)2.12H2O), iron (II) sulfate (FeSO4. 7H2O),
127 Manganese sulfate (MnSO4. 2H2O) were purchased from Sigma company (St. Loius, MO, USA).
128 Sulfuric acid (ZnSO4. 2H2O), Lead (II) nitrate (Pb(NO3)2. 2H2O), Chromium (III) nitrate (Cr
129 (NO3)3. 9H2O), HCl, sodium hydroxide (NaOH), MB and SO (Merck, Dermasdat, Germany)
130 used as received and their solutions were prepared by dissolving their appropriate amount in
131 double distilled water. In all stages, the pH was adjusted using pH/Ion meter model-686
132 (Metrohm, Switzerland, Swiss). Absorbance spectra of MB, SO (Fig. 1) were taken in a wide
133 range of wavelength (λ) from 400 to 750 nm, using UV–Visible spectrophotometer model V-530

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134 (Jasco, Japan) with a fixed slit width of 2 nm and scan speed of 1000 nm/min. Heavy metal ions
135 analysis was carried out by using flame atomic absorption spectrophotometer (FAAS) Varian
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136 model AA 240 (USA). The Fe3O4 nanoparticles were characterized by FESEM (Hitachi. S4160,
137 Japan), XRD (PW 1800, Philips, Germany) and A Fourier transform infrared (FT-IR) spectrum

Dalton Transactions Accepted Manuscript

138 was recorded using a Perkin Elmer-Spectrum-RX-IFT-IR spectrometer in the range of 400–4000
139 cm-1. Raman spectra were recorded in the backscattering geometry in the range 200–2000 cm-1
140 using a Handheld Raman Analyzer Raman spectrometer (model-™FIRSTGUARD, RIGAKU).
141 Particle size distribution of the samples was determined using a particle size Qudix, ScatterO
142 Scope (I) system (Korea) at 25 ˚C. An ultrasonic bath with heating system (Tecno-GAZ SPA
143 Ultra Sonic System, Parma, Italy) at 40 kHz of frequency and 130 W of power was used for the
144 ultrasound-assisted adsorption procedure. A HERMLE bench centrifuge (2206A, Germany) was
145 used to accelerate the phase separation.
146
147 2.2. Synthesis of Mn doped Fe3O4-NPs loaded on AC
148 The reaction solution for synthesis of Mn doped Fe3O4 nanoparticles was prepared as follows:
149 first 10 g of ammonium iron (III) sulfate, 5.0 g iron (II) sulfate solution and 5.0 g manganese
150 sulfate were dissolved (by 6 mL of concentrated sulfuric acid at pH= 2.4) and mixed thoroughly
151 in 20 mL deionized water. Then, 130 mL distilled water and 20 g activated carbon (AC) were
152 added to above solution and 140 mL of 1.5 mol L-1 sodium hydroxide was added drop-by-drop
153 during 70 minutes along with strong stirring at room temperature in an Erlenmeyer flask. After
154 70 minutes, again 100 mL of 3 mol L-1 sodium hydroxide solution was added to the mixed
155 reaction solution drop-by-drop during 40 minutes at room temperature. The prepared reaction
156 solution was stirred strongly for 27 hours at room temperature. The Mn doped Fe3O4-NPs loaded
157 on AC were filtered and washed several times by distilled water and dried at 35 ºC for 15 hours
158 and finally characterized and used as an absorbent for adsorptions experiments.
159
160 2.3. USA- adsorption method
161 The simultaneous removal of dyes and under study metal ions was examined using ultrasonic
162 power combined Mn-Fe3O4-NPs-AC. The adsorption experiment was assisted by the ultrasonic
163 waves and the influence of variables i.e. adsorbent mass, sonication time, initial SO, MB, Pb2+
164 and Cr3+ concentrations in quaternary system removal were examined and optimized values were

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165 found to be 0.025 g, 3 min, 20, 10, 38 and 42 mg L-1, respectively, at the desired temperature (25
166 ºC). At the end of the adsorption experiments, the sample was immediately centrifuged and the
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167 magnitude of non-adsorbed target compounds was analyzed via UV–Vis spectrophotometer
168 and/or flame atomic absorption spectrometry, respectively.

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169
170 2.4. Kinetics and adsorption isotherms
171 For this purpose 0.01, 0.015 and 0.02 g of adsorbent was contacted with 50 mL of analytes
172 solution at optimum conditions viz. ultrasonic at 25 ºC for different time intervals at pH 5.0. The
173 samples were filtered and analytes content were determined and experimental data at various
174 times were fitted to different models such as pseudo first, second-order, intraparticle diffusion
175 and elovich models. The experiments were also performed in the initial dyes and ions
176 concentrations range of 5–50 mg L-1 to obtain adsorption isotherms. A series of solutions with
177 different concentrations of understudy compounds were prepared by proper dilution of their
178 stock solution and 50 mL of each solution was mixed with 0.01, 0.015 and 0.02 g of Mn-Fe3O4-
179 NPs-AC and agitated for 3 min in ultrasonic at 25 ºC at pH 5.0. The samples were filtered and
180 the non-removed content of each species were quantified according to calibration curve achieved
181 at similar conditions. Finally, their equilibrium data were fitted to conventional isotherm models
182 like Langmuir, Freundlich, Temkin and Dubinin-radushkevich and the corresponding parameters
183 of each model were calculated from the respective graphs.
184
185 2.5. Measurements of dye uptake
186 The dye concentrations were determined according to calibration plots achieve at the same
187 conditions. The dyes and ions removal percentage (R %) was calculated using the following
188 equation:
189
C0 - C t
190 Percent removal. ( % ) = ×100% (1)
C0
191
192 Where C0 (mg L-1) and Ct (mg L-1) are the dye concentration at initial and after time t
193 respectively and the equilibrium adsorption capacity of dyes was calculated according to Eq. (2):
194

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195
(C 0 - C e )V
196 qe = (2)
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W
197
198 where C0 (mg L-1) and Ce (mg L-1) are the initial and equilibrium dye concentrations in solution,

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199 respectively, V (L) is the volume of the solution and W (g) is the mass of the adsorbent.
200
201 2.6. Response surface methodology (RSM)
202 Optimum conditions for the efficient and quantitative adsorption of target compounds onto Mn-
203 Fe3O4-NPs-AC were determined by means of central composite design (CCD) under RSM as
204 useful simultaneous optimization technique.39 There are three main steps involved in this
205 process: experimental design, modeling, and optimization. This model provides relatively few
206 combinations of variables for the determination of complex response function.40
207 A six-factor (A, B, C, D, E and F) and five-levels (-α, -1, 0, +1 and +α) CCD with minimum
208 number of experiments, while adsorbent mass (A. g), sonication time (B, min), MB
209 concentration (C, mg L-1), SO concentration (D, mg L-1), Pb2+ ions concentration (E, mg L-1) and
210 Cr3+ ions concentration (F, mg L-1) are used in optimization section. The dependent variable
211 (response variable) was the species removal percentages and each variable was coded five levels
212 (-α, low, central, high and +α; Table 1).
213 The minimum and maximum levels (Table 1) given to each factor were chosen based on
214 preliminary experiments. Each experiment was performed in double and the average values were
215 taken as the response (R %). Fitting and analysis of experimental data approximately follow
216 second-order polynomial model with acceptable estimated regression coefficients. The
217 generalized second order polynomial model proposed for the response surface analysis was given
218 as follows:
219
k k k k
220 y = β0 + ∑βi xi +∑∑βij xi x j + ∑βii xi2 + ε (3)
i=1 i=1 j=1 i=1

221
222 where y is the predicted response; Xi and Xj are the coded values of independent variables; and
223 β0, βi, βii and βij are the regression coefficients for intercept, linear, quadratic and interaction

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224 terms, respectively. ɛ represents the random error and k is the number of factors. In this
225 experiment, k=6. Data were processed for Eq. (3). Design-Expert program including ANOVA
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226 (Analysis of Variance) based on well-known F and P-value give very constructive and useful
227 information about main effect and interactions between variables and also their contribution on

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228 the response.
229 The goodness of fit of the quadratic model was expressed by the coefficient of determination R2,
230 and its statistical significance was checked by the Fisher's F-test in the same program. In the
231 present study a total of 32 runs were carried out to estimate the coefficients and lateral generated
232 mathematical model was validated by conducting experiments at optimal values of variables
233 predicted by response optimization.
234 The optimum values of selected variables were obtained by solving the regression equation and
235 by evaluating the response surface plots. The response surface plots are used for analysis of
236 different interaction between independent variables while keeping the value of the six variables
237 as constant. Such three dimensional plots give accurate geometrical representation and provide
238 useful information about the behavior of the system.
239
240 3. Results and discussion
241 3.1. Characterization of Mn doped Fe3O4 nanoparticles
242 FE-SEM image was used to determine the morphology and the particle size of the prepared Mn
243 doped Fe3O4-NPs (Fig. 2a) that suggest essentially spherical shaped particles with the
244 approximately size of 40 nm. The particles are almost uniform in the shape and the size.
245 The particle size frequency of the sample was measured by using particle size analysis technique
246 and shown in Fig. 2b. According to the obtained results the average size of particles was 124 nm.
247 Fig. 3a shows the XRD pattern of the prepared Fe3O4 nanoparticles. The six peaks observed in
248 diffractogram at 2θ= 30.1, 35.3, 43.1, 56.9, 62.10, and 70.5° are related to (220), (311), (400),
249 (511), (440), and (620) lattice planes of magnetite (Fe3O4) and/or maghemite (γ-Fe2O3),
250 respectively (JCPDS No.19-0652 and 04-0755), Because XRD patterns of maghemite (γ-Fe2O3)
251 and magnetite (Fe3O4) are practically identical,41 X-ray diffraction alone cannot be used to
252 distinguish between the two phases. Therefore, we employed Raman spectrophotometry
253 technique to distinguish between these two phases. In the XRD pattern, no characteristic peaks of
254 impurity phases such as Fe(OH)2 and/or Fe(OH)3 were detected.

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255 Raman spectroscopy can effectively distinguish between maghemite and magnetite
256 nanoparticles. Raman spectrum of the prepared sample was shown in Figure 3b. Raman features
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257 of Fe3O4 are sample specific, depending on non-stoichiometry, cation distribution, defects, and
258 also on the experimental conditions. Nevertheless, the Raman spectra of magnetite are distinct
from those obtained from maghemite.42 Mandal et al 43 reported the presence of distinct peaks at

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259
260 283 cm−1,490 and 668 cm-1 for undoped Fe3O4 nanoparticles, which correspond to the Eg, T2g
261 and Ag modes, respectively. Besides, in the published reports, in the Raman spectra the
262 characteristic peaks of the Fe3O4 appeared at 668, 540, 450-500, 350 and 306 cm-1,42 whereas γ-
263 Fe2O3 shows broad bands around 700 and 500 cm-1 and α-Fe2O3 shows the resonant peaks at 225,
264 245, 291, 410, 611 and 1318 cm-1. 42-45
265 In our study, the Raman spectrum of the prepared sample (Fig. 3b) shows three peaks at 438,
266 455, and 479 cm-1. The results were compared with the different published results and assigned
267 as T2g mode of symmetry of Fe3O4, while the peaks at 500, and 700 cm−1 belonging to γ-Fe2O3
268 as well as the peaks related to α-Fe2O3 were not observed in our results.42-45 Therefore, the
269 Raman analysis confirmed that the chemical composition of the prepared sample in this
270 experiment is Fe3O4. The rather weak peak at 1620 cm−1 is related to the δ(H2O) mode.
271 The FT-IR spectrum of the prepared Mn doped Fe3O4-NPs (Fig. 3c) indicate strong and broad
272 absorption bands at 530 cm-1 and 431 cm-1 are assigned to Fe-O stretching and bending vibration
273 modes of Fe3O4, respectively.46 The strong and broad absorption peaks about 3200-3375 cm-1
274 and 1600 cm-1 are attributed to normal polymeric O-H stretching vibration and H-O-H bending
275 vibration of H2O adsorbed in the Fe3O4 lattice,46, 47 respectively.
276
277 3.2. Effect of pH
278 Solution pH is serious effective parameters in controlling adsorption seems with important
279 influences on the solubility and chemistry, charge and abundance of metal ions, surface charge of
280 adsorbent, dissociation and/or protonation of analytes and adsorbent functional groups.48 Typical
281 results assigned to effect of pH on the removal efficiency (%) of Pb2+ ions illustrated in Fig. 4a.
282 Owing to the fact in pH less than 3 due to formation of positive charge simultaneously on
283 adsorbent and metal ions and in pH higher than 7 due to formation of hydroxide complex or
284 probable precipitation as hydroxide form an expectable reduce in removal efficiency was
285 observed. Increasing pH from 2 to 5 for Pb2+ ions cause removal percentage raising from 40-60%

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286 to 97.08% and the adsorption capacity increased. Result also reveal that for Cr3+ ions removal
287 percentage was highly pH-dependent and increases with increasing solution pH. At pH < 4.0, the
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288 Cr3+ ions adsorption was increased slowly and reaches its maximum value at pH 4.0-5.5 and
289 subsequently reach plateau. At low pH, competition among proton and Cr3+ ions for the same
binding sites of adsorbent lead to reduce in removal percentage.26 Rising the pH, lead to enhance

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290
291 in the number of negative charge sites of adsorbent that facilitate the adsorption of cationic Cr3+
292 ions. Fig. 4a shows the adsorption process as pH function and reveal that adsorption favored at
293 higher pH and suggest presence of more negative charged sites available on adsorbent which
294 accelerate adsorption through electrostatic attraction and/or complexation, while the percentage
295 of hydrolyzed Cr3+ ions increased.49 The neutral pH was found to be optimum for the MB and
296 SO adsorption. At lower pH, adsorption of high content of proton on adsorbent surface leads to
297 the generation of net positive charge, which increases electrostatic repulsive force and thus
298 decreases the adsorption of MB and SO molecules. At 5.0-7.0 pH which is the working pH in
299 this research maximum removal percentage was seen. In compromise to achieve maximum
300 removal percentage for all species pH was set at approximate 5.0.
301
302 3.3. Statistical analysis
303 The CCD and corresponding results of RSM experiments in the following interval of variable: A
304 (0.01-0.03 g), B (2-6 min), C (5-25 mg L-1), D (5-25 mg L-1), E (20-60 mg L-1) and F (20–60 mg
305 L-1) on removal percentages of compounds are given in Table 1. The design suggested the
306 second-order polynomial model for the responses selected on the basis of the sequential model
307 sum of squares where the additional terms were significant and the models were not aliased. The
308 ‘‘Predicted R-Squared’’ was close to ‘‘Adjusted R-Squared’’. The quality of model was justified
309 based on the R2 and standard deviation values (Table S1). The ratio for the % RMB, % RSO, %
310 RPb2+ and %RCr3+ responses were 17.65, 34.24, 16.35 and 22.21, respectively. Their value greater
311 than 4 confirms the adequacy of model for representation of experimental data.
312 The removal percentage results in second-order response surface by ANOVA (Tables 2 and 3)
313 demonstrate that all the models were significant at the 5% confidence level (P-values less than
314 0.05). The R2 value close to unity and lower standard deviation strongly support high
315 performance of method in term of larger accuracy and repeatability of model for prediction of
316 real behavior of adsorption system. The values of coefficient of determinations (R2= 0.989,

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317 0.997, 0.991 and 0.995) obtained in the present study for %RMB, %RSO, %R Pb2+ ions and % RCr3+
318 responses were higher than 0.80 as minimum acceptable value.
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319 A high R2 value close to 1 demonstrates good agreement between the calculated and observed
320 results within the range of experiment and also has desirable and reasonable trend with adjusted
R2.50 The data were analyzed to examine the correlation between the actual or experimental and

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321
322 predicted responses for dyes and ions (Fig. 4b). The data points were well distributed close to a
323 straight line with the R2 values of 0.989, 0.997, 0.991 and 0.995 for %RMB, %RSO, %R Pb2+ ions
324 and % RCr3+, respectively (excellent relation among experimental and predicted values).51
325 Tables 2 and 3 gives ANOVA results for respective responses and based on well-known
326 phenomena the highly significant regression model is justified by higher Fischer’s ‘F statistics’
327 values with ‘P’ value (probability) as low as possible.52
328 The variables denoted in ANOVA (Table 2 and 3) were the main effects, the interaction effects,
329 and the error terms. F and p-values were used to represent the importance of these variables in
330 the quadratic model. In addition, the sum of squares (SS), degrees of freedom (DF), and mean
331 squares (MS) were calculated. The F-value was obtained by dividing MS by DF, whereas the MS
332 value obtained by dividing SS by DF.53
333 The Model F-value of 12.92, 52.78, 16.51 and 27.24 for removal of MB, SO, Pb2+ and Cr3+ ions,
334 respectively, implies the goodness and usefulness of presented model. Moreover, the quality of
335 fitness models was assessed by a lack-of-fit test (p > 0.05 for all responses); this test determines
336 model accuracy to predict variation. The high reliability and precision of the response data were
337 confirmed by values of coefficient of variation (CV %) that varied between 0.610-3.221.
338 Adequate precision is a statistical index that indicates signal to noise ratio; values higher than 4
339 are acceptable. For all responses studied, this indicator is greater than 4 (Table S1).
340 The ‘F’ and ‘P’ values (Tables 2 and 3) using standardized main effect Pareto charts (P = 95%)
341 and two factor interaction Pareto charts (P = 95%) (Fig. S1) reveal that the factors of A, B and
342 the quadratic effect of A2 are the most effective factors and thus the empirical equation are as
343 follows:
344
y MB = 126.8 + 502.4A +1.6052 B - 0.434 C +16.9 AC + 9.29 AF -
345 (4)
0.0225 CD + 0.0202 CF + 0.037 DE - 305 A 2 + 0.0033 E 2 + 0.004 F2
346

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ySO = 99.26 + 5666 A + 0.455 B - 6.8 D +117.1 AC +193.21AD - 0.16 BE

347 (5)
+0.22 BF - 0.111 CD - 0.064 CE + 0.0583 CF + 0.132 DE-226549.6 A 2
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348
y Pb2+ = -39.294 + 3802.2 A -13.756 B +1.0048 C + 5.4 D + 2.62 E - 0.0185 EF -
349 (6)
0.017 E 2

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350
y Cr3+ = -49.3 + 2158.6 A + 7.84 B +1.93 E + 0.832 F -1122 AB + 72.7 AE +
351 (7)
89 AF + 0.89 BD + 0.51 BE - 0.25 DE - 90812 A 2 -1.6 B2 - 0.03 E 2 - 0.04 F2
352
353 3.4. Effect of variables and response surface 3D plots
354 Figs. 5 and 6 demonstrate the fitted response surface and contour plots of removal (%) across
355 important variables. The bents nature of curves is good indication of interaction between the
356 parameters.
357 According to Figs. 5 (a, b) and 6 (a), the response surface plots show the relation among initial
358 analytes concentration and amount of adsorbent, while the initial pH and sonication time were
359 kept constant at 5 and 4 min (the central levels), respectively. The increase in analytes removal
360 efficiency with rising adsorbent mass (Figs. 5 and 6) is emerged from the higher available
361 surface area of adsorbent.
362 It was evident that the adsorption efficiency considerably increased with an increase in adsorbent
363 dose due to its high effective surface area for adsorption. At lower amount of adsorbent, the
364 removal percentage significantly decreased because of high ratio of analytes molecules to vacant
365 site of adsorbent.
366 Figs. 5(c) and 6(c) shows the interaction of adsorbent mass with sonication time and their
367 relation with removal percentage. The maximum adsorption of analytes achieved in high
368 sonication time that confirm strong association of ultrasound in mass transfer. The results show
369 that the initial adsorption rate is very rapid because of high available surface area and vacant site
370 of adsorbent that accelerated by enhance in mass transfer by ultrasonic power.
371 It may be seen from the figures (Figs. 5c and 6c) that the increase in amount of adsorbent dose
372 leads to significant decrease in sonication time. On the other hand, percentage dye removal was
373 increased with the amount of adsorbent for a particular sonication time.

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374 Fig. 6(b) clearly indicates that as the adsorbent mass and sonication time increases, the
375 adsorption efficiency improves. It could be explained by the fact that the more amounts of Mn-
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376 Fe3O4-NPs-AC cause an increase in the adsorbent surface as well as active surface. The active
377 surfaces prepare some spaces for capturing Cr3+ ions molecules and increasing these spaces
makes the Cr3+ get out faster.

Dalton Transactions Accepted Manuscript

378

379
380 3.5. Optimization of dyes and ions adsorption
381 In the numerical optimization, a minimum and a maximum level must be provided for each
382 parameter. A multiple response method or optimization of any combination of six objectives
383 namely A, B, C, D, E and F was applied. Fig. 7 and Table S2 results illustrate the ranges of
384 parameters obtained from the model (their exact value shown by the circles). The bottom lines
385 show the recovery of dyes and ions at horizontal range. By optimizing the process parameters to
386 obtain maximum removal of MB, SO, Pb2+ and Cr3+ ions under these conditions: adsorbent mass
387 = 0.025 g, sonication time = 3 min, MB concentration = 20 mg L-1, SO concentration = 10 mg L-
1
388 , Pb2+ ions concentration = 38 mg L-1 and Cr3+ ions concentration = 42 mg L-1, maximum
389 removal of 99.54% for MB, 98.88% for SO, 80.25% for Pb2+ and 99.54% for Cr3+ was achieved.
390
391 3.6. Kinetics of dyes and ions adsorption onto Mn-Fe3O4-NPs-AC
392 In the present study, the appropriate kinetic model was investigated for explaining the nature of
393 adsorption process. To investigate the mechanism of adsorption and rate controlling steps such as
394 chemical reaction and diffusion control, conventional kinetic models including pseudo-first-
395 order, pseudo-second-order, intraparticle diffusion and Elovich were used.
396 The pseudo-first-order kinetic model known as the Lagergren 54 equation is given as:
397
k1
398 log(q e – q t ) = logq e – ( )t (8)
2.303
399
400 where qe and qt refer to the amount of analytes (mg g-1) at equilibrium and at any time,
401 respectively and k1 is the equilibrium rate constant of pseudo-first-order adsorption (min-1). The
402 plot of log (qe-qt) vs. t should give a linear relationship which the value of k1 was determined
403 from the slope of the plot (Table 4).
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404 The results show (Table 4) that the theoretical qe (calc) value does not agree to the experimental
405 qe (exp) values at all concentrations studied with poor correlation coefficient. So, further the
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406 experimental data were fitted with second order Lagergren model.
407 The pseudo-second-order rate equation developed by Ho and McKay assumes that the adsorption
capacity of adsorbent is directly proportional to the number of active sites on its surface.55 The

Dalton Transactions Accepted Manuscript

408
409 pseudo-second-order rate expression is given as:
410

t 1 t
411 = 2
+ (9)
q t k 2q e q e
412
413 where k2 (g mg-1 min-1) is the equilibrium rate constant for the pseudo-second-order adsorption
414 and can be obtained from the plot of t/qt against t (Table 4).
415 The adsorbate species are most probably transported from the bulk of the solution into the solid
416 phase with an intraparticle diffusion process with general applicability as rate-limiting step in
417 many adsorption processes which can be explained by following well known equation:10
418

419 q t = K dif t1/ 2 + C (10)

420
421 where C is the intercept and Kdif is the intra-particle diffusion rate constant. The values of Kdif (g
422 mg-1 min-1/2) and C and the corresponding linear regression correlation coefficient R2 are given
423 in Table 4.
424 The applicability of intraparticle diffusion model imply that adsorption process of the dyes was a
425 complex process involving both boundary layer and intraparticle diffusion.
426 The constant C was found to increase from 17.960 to 170.48 with increase in analytes amount
427 from 10 to 42 mg L-1 at 0.01–0.02 g of Mn-Fe3O4-NPs-AC. A larger C value indicates a greater
428 effect of the boundary layer.
429 This change in C value is belong to increase in thickness of the boundary layer and decrease the
430 chance of the external mass transfer and subsequently prominent increase in the amount of
431 internal mass transfer. The high value of R2 shows suitability of this model to explain the
432 experimental data. This may confirm that the rate-limiting step is the intraparticle diffusion
433 process.
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434 The Elovich equation is useful in describing adsorption on highly heterogeneous adsorbent. The
435 Elovich 56 model is given by:
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436
1 1
437 q t = ln(αβ) + lnt (11)
β β

Dalton Transactions Accepted Manuscript

438
439 The qt is a linear function of ln (t) if the Elovich would apply where β and α would be obtained
440 from the slope and intercept of the plot of the Elovich equation, respectively.
441 The Elovich constants obtained from the slope and the intercept of the straight line are reported
442 in Table 4. The low correlation coefficient of this model shows the unsuitability of it for
443 evaluation of the adsorption process.
444 The kinetic constants and correlation coefficients of the pseudo-first-order, pseudo-second-order,
445 intraparticle diffusion and elovich are presented in Table 4. At all concentrations and adsorbent
446 amount, the calculated qe values were mainly closer to the experimental data and the R2 values
447 for pseudo-second-order kinetic model were larger than that of pseudo-first-order model. These
448 two simultaneous trends reveal the pseudo-second order model is more suitable for describing
449 the adsorption behavior of dyes and ions onto Mn-Fe3O4-NPs-AC. Generally, the intraparticle
450 diffusion model possesses two parts that are attributed to phenomena such as initial surface
451 adsorption and subsequent intraparticle diffusion. The R2 value (Table 4) for this model was near
452 from the unity, which shows that the intraparticle diffusion model is applicable.
453
454 3.7. Adsorption isotherms
455 Langmuir isotherm57 is based on adsorption on homogeneous sites as monolayer with uniform
456 strategies with no transmigration of adsorbate in the plane of the surface. The linear form of
457 Langmuir isotherm equation is given as:
458
Ce 1 C
459 = + e (12)
qe QmkL Qm
460
461 where Ce is the equilibrium concentration of adsorbate (mg L-1); qe is the adsorption capacity (mg
462 g-1); kL and Qm are the Langmuir constants. The values of Langmuir constants kL and Qm were

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463 calculated from the slope and intercept of the linear plot of Ce/qe versus Ce.
464 The fitness of experimental data was evaluated at different levels of adsorbent dosage. The high
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465 correlation coefficient (0.993-0.999) at all adsorbent dosage and high maximum monolayer
-1
466 capacity (91.99-267.4 mg g using 0.01-2.0 g adsorbent) show the applicability of Langmuir

Dalton Transactions Accepted Manuscript

467 model for interpretation of the experimental data over the whole concentration ranges.
468 The essential feature of the Langmuir isotherm can be expressed in terms of dimensionless
469 constant separation or equilibrium parameter (RL), which is defined as:
470
1
471 RL = (13)
1+ K L C 0
472
473 where C0 is the initial analyte concentration (mg L-1) and b is the Langmuir constant. The value
474 of RL calculated from different initial concentrations is reported in Table 5. The value of RL
475 indicates the type of the isotherm to be either unfavorable (RL > 1), linear (RL = 1), favorable (0
476 < RL < 1) or irreversible (RL = 0).58 The obtained RL values for dyes and ions between 0.009 and
477 0.230 suggest favorable adsorption of target compounds on Mn-Fe3O4-NPs-AC.
478 The following linear Freundlich 59 equation was applied for fitting the experimental data.
479

480 lnq e = lnK F + 1 lnCe (14)

n
481
482 where 1/n and KF are the Freundlich adsorption isotherm constant and its respective correlation
483 coefficient, respectively. The intercept and slope of linear plot of ln (qe) versus ln (Ce) give the
484 values of KF and 1/n, respectively. The Freundlich constants were calculated and presented in
485 Table 5.
486 The correlation coefficients (0.910–0.985) and higher error value of this model show that the
487 Freundlich model has lower efficiency compared to the Langmuir model.
488 The heat of the adsorption and the adsorbent–adsorbate interaction were evaluated by using
489 Temkin isotherm model:60
490
491 q e = B1 ln K T + B1 ln Ce (15)
492
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493 B1 is the Temkin constant related to heat of the adsorption (J mol-1), T is the absolute temperature
494 (K), R is the universal gas constant (8.314 J mol -1 K-1), KT is the equilibrium binding constant (L
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495 mg-1).
496 The correlation coefficients R2 obtained from Temkin model were comparable to that obtained

Dalton Transactions Accepted Manuscript

497 for Langmuir and Freundlich equations, which explain the applicability of Temkin model to the
498 adsorption of dyes and ions onto adsorbent.
499 In order to calculate the mean free energy value of sorption, Dubinin–Radushkevich (D-R)
500 isotherm has also been applied for the sorption of dyes and ions onto Mn-Fe3O4-NPs-AC. The D-
501 R equation can be defined by the following equation:61
502

503 ln q e = lnQ s - B ε 2 (16)

504
505 where B is the constant related to sorption energy (mol2 J-2), QS is the D–R monolayer capacity
506 (mol g-1), qe is the amount of dye and ion sorption per unit weight of Mn-Fe3O4-NPs-AC (mg g-1),
507 ε is the Polanyi potential which can be obtained as follows:
508
1
509 ε = RT ln (1+ ) (17)
Ce
510
511 where Ce is the equilibrium concentration of dyes and ions (mol L-1), R gas constant and T the
512 temperature (K). By plotting ln qe versus ε2, it is possible to determine the value of B from the
513 slope and the value of QS from the intercept, which is ln QS.
514 The lower R2 values (0.845–0.981) over the whole adsorbent dosage show unsuitability of D–R
515 model for fitting the experimental data. In this case, the D–R equation represents the poorer fit of
516 the experimental data than other isotherm equations.
517 The mean free energy E (kJ mol-1) of sorption can be estimated by using B values as expressed in
518 the following equation:62
519
1
520 E= (18)
2B
521

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522 The parameters obtained using above equations was summarized in Table 5 that suggest physical
523 adsorption (mean free energy value is lower than 8 kJ mol-1). Since E values are in the range of
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524 2-7 kJ mol-1 at 0.01, 0.015 and 0.02 g of adsorbent, indicating that the adsorption process of dyes
525 and ions were probably controlled as physically.

Dalton Transactions Accepted Manuscript

526 Langmuir isotherm fits the data better than Freundlich, Temkin and D-R isotherms which
527 justified by its higher R2 value (>0.993) that support more abundance for occurrence of
528 understudy compound adsorption onto Mn-Fe3O4-NPs-AC takes place as monolayer sorption on
529 a surface that is homogenous in sorption affinity.
530 The values of the Temkin constants and the correlation coefficient are lower than the Langmuir
531 value. Therefore, the Temkin isotherm represents a worse fit of experimental data than the
532 Freundlich isotherm but the Langmuir isotherm provides the best correlation for the experimental
533 data.
534 As can be seen from Table 5, Mn-Fe3O4-NPs-AC sorbent used in this work has a relatively large
535 sorption capacity in single component (229.4 mg g-1 for MB, 159.7 mg g-1 for SO, 139.5 mg g-1
536 for Pb2+ ions and 267.4 mg g-1 for Cr3+ ions) for the removal of dyes and ions from aqueous
537 solution compared to some other sorbents reported in the literature in Table 6.
538
539 3.8. Comparison with other methods
540 The maximum sorption capacity Qmax (mg g-1) is great criterion for judgment useful in scale-up
541 considerations. Some studies have been conducted using various types of sorbents for MB, SO,
542 Pb2+ and Cr3+ adsorption.12, 26, 30, 63-80 Table 6 presents a comparison of the sonication time and
543 sorption capacity of Mn-Fe3O4-NPs-AC with that reported for other sorbents. It can be seen from
544 Table 6 that the adsorbent show a comparable sorption capacity with the respect to other
545 sorbents, revealing that the Mn-Fe3O4-NPs-AC is suitable for the removal of dyes and ions from
546 aqueous solutions since it has a relatively high sorption capacity.
547
548 4. Conclusion
549 The dyes and heavy metals is commonly released into the environment through wastewaters
550 disposed from industries. Therefore, dyes and ions remediation prior to discharge is of great
551 importance. Application of Mn-Fe3O4-NPs-AC could be as an effective adsorbent for removing
552 the MB, SO, Pb2+ and Cr3+ from contaminated water resources. This study tried to synthesize and

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553 characterize the new class of adsorbent examine their performance on MB, SO, Pb2+ and Cr3+
554 removal from aqueous solution using CCD under the RSM. Several parameters such as the
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555 adsorbent mass, sonication time, initial dyes concentration and initial ions concentration were
556 investigated. The obtained results demonstrated the empirical models were satisfactorily (p <

Dalton Transactions Accepted Manuscript

557 0.001) fitted to the experimental data. All mathematical equations developed in this process
558 demonstrated high determination coefficients (greater than 0.988) and insignificant lack of fit (p
559 > 0.05). The optimum removal efficiency of MB, SO, Pb2+ and Cr3+ achieved by setting the
560 experiment with adsorbent mass at 0.025 g, sonication time at 3 min, initial MB concentration at
561 20 mg L-1, initial SO concentration at 10 mg L-1, initial Pb2+ concentration at 38 mg L-1 and
562 initial Cr3+ concentration of 42 mg L-1. Results also prove that the RSM is a powerful tool for
563 optimizing the operational conditions of dyes and ions removal efficiency using adsorbent.
564 Conventional kinetic models were applied and it was seen that pseudo-second-order equation is
565 suitable to fit the experimental data. Analysis of experimental equilibrium data to the Langmuir,
566 Freundlich, and Temkin and Dubinin-Radushkevich isotherms shows that the Langmuir is the
567 best model for the dyes and ions interpretation of equilibrium data. The obtained results
568 demonstrated that adsorbent can promisingly be used as an efficient sorbent for dyes and heavy
569 metals.
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584

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585 References
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728 57. I. Langmuir, J. Am. Chem. Soc., 1916, 38, 2221-2295.
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730 58. A. A. Khan, R. Ahmad, A. Khan and P. K. Mondal, Arab. J. Chem., 2013, 6, 361-368.
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734 60. M. Temkin and V. Pyzhev, Acta Physicochim. U. R. S. S., 1940, 12, 217-222.
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736 61. M. Dubinin and L. Radushkevich, Chem. Zentr., 1947, 1, 875-889.
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742 64. M. Roosta, M. Ghaedi, A. Daneshfar, R. Sahraei and A. Asghari, Ultrason. Sonochem., 2014,
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745 65. M. Ghaedi, S. Heidarpour, S. Nasiri Kokhdan, R. Sahraie, A. Daneshfar and B. Brazesh,
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758 70. S. Shariati, M. Faraji, Y. Yamini and A. A. Rajabi, Desalination, 2011, 270, 160-165.
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767 74. Y.-H. Li, Q. Du, X. Peng, D. Wang, Z. Wang, Y. Xia and B. Wei, Colloid. Surf. B:
768 Biointerfaces, 2011, 85, 316-322.
769
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770 75. M. Iqbal and R. Edyvean, Mineral. Eng., 2004, 17, 217-223.
771
772 76. M. Rashid and F. Khan, J. Water Process Eng., 2014, 3, 53-61.

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773
774 77. M. Deravanesiyan, M. Beheshti and A. Malekpour, J. Ind. Eng. Chem., 2015, 21, 580-586.
775
776 78. A. Demirbaş, Energy sources, 2005, 27, 1449-1455.
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DOI: 10.1039/C5DT01504A

813 Table. 1. Experimental factors and levels in the central composite design.
Levels
Factors -α Low (-1) Central (0) High (+1) +α
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A: Adsorbent mass (g) 0.01 0.015 0.02 0.025 0.03

B: Sonication time (min) 2 3 4 5 6
-1
C: MB concentration (mg L ) 5 10 15 20 25
D: SO concentration (mg L-1)

Dalton Transactions Accepted Manuscript

5 10 15 20 25
E: Pb2+ concentration (mg L-1) 20 30 40 50 60
F: Cr3+ concentration (mg L-1) 20 30 40 50 60
Factors R%
Run A B C D E F MB SO Pb2+ Cr3+
1 0.0150 3.00 10.00 10.00 30.00 30.00 98.43 87.72 66.00 94.41
2 0.0250 3.00 20.00 20.00 30.00 50.00 99.44 94.48 76.33 99.71
3 0.0150 5.00 10.00 20.00 50.00 50.00 97.54 83.82 53.20 84.22
4 0.0150 5.00 10.00 10.00 30.00 50.00 98.39 91.07 70.00 54.64
5 0.0250 5.00 10.00 10.00 50.00 50.00 98.50 90.68 61.40 98.86
6 0.0200 4.00 15.00 15.00 60.00 40.00 99.08 94.34 53.67 78.85
7 0.0250 3.00 20.00 10.00 50.00 50.00 99.33 93.82 67.40 97.29
8 0.0300 4.00 15.00 15.00 40.00 40.00 99.00 93.81 82.50 84.81
9 0.0200 4.00 15.00 15.00 40.00 40.00 98.12 94.64 72.00 99.91
10 0.0150 3.00 20.00 20.00 50.00 50.00 93.79 69.01 56.00 42.06
11 0.0200 4.00 15.00 15.00 20.00 40.00 98.03 90.39 80.00 98.13
12 0.0250 3.00 10.00 10.00 50.00 30.00 98.64 92.04 71.60 100.0
13 0.0100 4.00 15.00 15.00 40.00 40.00 89.36 47.88 66.75 96.56
14 0.0150 5.00 20.00 20.00 50.00 30.00 91.46 60.22 58.80 100.0
15 0.0250 5.00 10.00 20.00 30.00 50.00 96.98 93.27 75.33 89.36
16 0.0200 4.00 15.00 5.000 40.00 40.00 99.03 87.96 62.25 100.0
17 0.0200 4.00 15.00 15.00 40.00 60.00 98.99 93.21 78.00 95.36
18 0.0150 3.00 20.00 10.00 30.00 50.00 98.51 90.09 72.33 67.96
19 0.0200 2.00 15.00 15.00 40.00 40.00 97.32 95.64 69.75 100.0
20 0.0200 4.00 15.00 15.00 40.00 40.00 98.01 94.97 72.50 99.06
21 0.0200 4.00 15.00 25.00 40.00 40.00 97.50 87.02 48.75 99.73
22 0.0200 4.00 5.000 15.00 40.00 40.00 97.68 93.37 65.00 100.0
23 0.0200 4.00 15.00 15.00 40.00 40.00 97.70 92.92 70.75 100.0
24 0.0200 4.00 15.00 15.00 40.00 40.00 97.85 92.55 71.50 98.91
25 0.0250 3.00 10.00 20.00 30.00 30.00 97.00 91.53 72.67 97.36
26 0.0250 5.00 20.00 10.00 50.00 30.00 98.97 90.66 65.40 97.78
27 0.0250 5.00 20.00 20.00 30.00 30.00 98.58 93.87 72.33 100.0
28 0.0150 5.00 20.00 10.00 30.00 30.00 98.28 90.99 70.00 98.28
29 0.0150 3.00 10.00 20.00 50.00 30.00 98.83 91.24 58.80 62.15
30 0.0200 4.00 25.00 15.00 40.00 40.00 98.22 92.52 79.50 100.0
31 0.0200 6.00 15.00 15.00 40.00 40.00 99.19 92.86 68.00 94.11
32 0.0200 4.00 15.00 15.00 40.00 20.00 98.53 92.65 69.50 97.93
814
815
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817 Table. 2. Analysis of variance (ANOVA) for removal dyes.

Response R% MB R% SO
a b c
Source SS Df MS F-value P-value SS Df MS F-value P-value
Model 123.7145 27 4.582019 12.91716 0.00145 3484.166 27 129.0432 52.78445 0.0007490

Dalton Transactions Accepted Manuscript

A 46.544 1 46.54400 131.2121 0.0003315 1054.908 1 1054.908 431.5046 < 0.0001
B 4.119943 1 4.119943 11.61452 0.02708 30.55118 1 30.55118 12.4968 0.02412
C 5.98407 1 5.984070 16.86967 0.01477 0.358729 1 0.358729 0.146736 0.7212
D 1.178884 1 1.178884 3.323389 0.1424 59.80826 1 59.80826 24.46426 0.007783
E 0.552322 1 0.552322 1.557049 0.2802 7.773372 1 7.773372 3.179657 0.1491
F 0.106585 1 0.106585 0.300473 0.6127 0.15794 1 0.15794 0.064604 0.8119
AB 0.181894 1 0.181894 0.512778 0.5135 6.964241 1 6.964241 2.848686 0.1667
AC 2.845478 1 2.845478 8.02168 0.04724 137.1348 1 137.1348 56.09428 0.001700
AD 0.889477 1 0.889477 2.507523 0.1885 124.4292 1 124.4292 50.89709 0.002041
AE 0.498979 1 0.498979 1.406669 0.3012 1.287371 1 1.287371 0.526592 0.5082
AF 3.455367 1 3.455367 9.741016 0.03549 0.340547 1 0.340547 0.139299 0.7279
BC 0.145271 1 0.145271 0.409534 0.5570 0.679027 1 0.679027 0.277752 0.6261
BD 0.112723 1 0.112723 0.317778 0.6030 17.68462 1 17.68462 7.233803 0.05468
BE 0.095114 1 0.095114 0.268136 0.6319 42.62158 1 42.62158 17.43413 0.01397
BF 1.227527 1 1.227527 3.460517 0.1364 25.30154 1 25.30154 10.34946 0.03237
CD 5.060833 1 5.060833 14.26698 0.01948 122.7055 1 122.7055 50.19203 0.002096
CE 2.70921 1 2.709210 7.637525 0.05066 155.7337 1 155.7337 63.70206 0.001336
CF 5.429844 1 5.429844 15.30726 0.01736 45.31502 1 45.31502 18.53587 0.01259
DE 17.77095 1 17.77095 50.09802 0.002103 232.0418 1 232.0418 94.91548 0.0006217
DF 1.140118 1 1.140118 3.214104 0.1475 0.404426 1 0.404426 0.165428 0.7050
EF 1.675489 1 1.675489 4.723367 0.09545 0.168039 1 0.168039 0.068736 0.8061
A2 16.90845 1 16.90845 47.66656 0.002308 933.1771 1 933.1771 381.7112 < 0.0001
B2 0.494916 1 0.494916 1.395215 0.3030 0.368976 1 0.368976 0.150928 0.7174
C2 0.145903 1 0.145903 0.411316 0.5562 0.56262 1 0.56262 0.230137 0.6565
D2 1.942125 1 1.942125 5.47504 0.07939 1.846224 1 1.846224 0.755188 0.4339
E2 3.214546 1 3.214546 9.062118 0.03954 2.341387 1 2.341387 0.957732 0.3832
F2 4.248818 1 4.248818 11.97783 0.02580 0.592826 1 0.592826 0.242492 0.6482
Residual 1.418894 4 0.354724 9.778881 4 2.44472
Lack of Fit 0.966104 1 0.966104 6.401005 0.08542 3.759919 1 3.759919 1.874037 0.2645
Pure Error 0.45279 3 0.150930 6.018962 3 2.006321
Cor Total 125.1334 31 3493.945 31
818 a
Sums of Squares
819 b
Degrees of Freedom
820 c
Mean Square

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821 Table. 3. Analysis of variance (ANOVA) for removal ions.

Response R% Pb2+ R% Cr3+
Source SS Df MS F-value P-value SS Df MS F-value P-value
Model 2171.03 27 80.40852 16.51447 0.007185 5722.358 27 211.9392 27.2431 0.002737

Dalton Transactions Accepted Manuscript

A 124.0313 1 124.0313 25.47381 0.007246 69.0228 1 69.0228 8.872333 0.04079
B 57.78125 1 57.78125 11.86724 0.02618 61.73938 1 61.73938 7.936107 0.04797
C 78.125 1 78.125 16.04548 0.01605 0.000 1 0.000 0.000 1.0000
D 91.125 1 91.125 18.71545 0.01239 0.03753 1 0.03753 0.004824 0.9480
E 346.7222 1 346.7222 71.21056 0.001080 185.8963 1 185.8963 23.89549 0.008112
F 36.125 1 36.125 7.41943 0.05278 353.0382 1 353.0382 45.38026 0.002530
AB 9.61 1 9.61 1.973722 0.2328 503.4645 1 503.4645 64.71636 0.001296
AC 4.694444 1 4.694444 0.964155 0.3817 3.5072 1 3.5072 0.450823 0.5387
AD 10.95704 1 10.95704 2.25038 0.2080 27.92378 1 27.92378 3.58938 0.1311
AE 23.14815 1 23.14815 4.754217 0.09470 70.37897 1 70.37897 9.046658 0.03964
AF 0.017778 1 0.017778 0.003651 0.9547 316.8255 1 316.8255 40.7254 0.003094
BC 29.45333 1 29.45333 6.049189 0.06973 2.781847 1 2.781847 0.357584 0.5821
BD 2.56 1 2.56 0.525778 0.5085 317.1275 1 317.1275 40.76422 0.003088
BE 14.69444 1 14.69444 3.017977 0.1573 416.8157 1 416.8157 53.57835 0.001853
BF 34.00333 1 34.00333 6.983678 0.05742 1.091994 1 1.091994 0.140367 0.7269
CD 0.444444 1 0.444444 0.091281 0.7776 2.341538 1 2.341538 0.300986 0.6124
CE 1.21 1 1.21 0.248512 0.6443 33.37007 1 33.37007 4.289457 0.1071
CF 16.72454 1 16.72454 3.434921 0.1375 22.5629 1 22.5629 2.900281 0.1638
DE 0.668981 1 0.668981 0.137397 0.7297 820.5987 1 820.5987 105.4814 0.0005068
DF 0.001111 1 0.001111 0.000228 0.9887 0.355958 1 0.355958 0.045756 0.8411
EF 54.76 1 54.76 11.24673 0.02847 25.07777 1 25.07777 3.223548 0.1470
A2 2.104395 1 2.104395 0.432205 0.5468 149.941 1 149.941 19.27373 0.01178
B2 0.055153 1 0.055153 0.011327 0.9204 70.09208 1 70.09208 9.009781 0.03988
C2 0.162729 1 0.162729 0.033422 0.8638 0.100438 1 0.100438 0.01291 0.9150
D2 592.3135 1 592.3135 121.6506 0.0003841 0.017479 1 0.017479 0.002247 0.9645
E2 82.0044 1 82.0044 16.84224 0.01481 231.2544 1 231.2544 29.72591 0.005499
F2 0.073335 1 0.073335 0.015062 0.9082 415.504 1 415.504 53.40974 0.001864
Residual 19.47589 4 4.868972 31.11822 4 7.779555
Lack of Fit 6.179014 1 6.179014 1.39409 0.3228 23.31108 1 23.31108 8.957605 0.05800
Pure Error 13.29688 3 4.432292 7.807137 3 2.602379
Cor Total 2190.506 31 5753.476 31
822

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823 Table. 4. Kinetic parameters obtained from the simultaneous removal of dyes and ions by Mn-Fe3O4-NPs-AC under different
824 experimental conditions.
Model First-order- kinetic Second-order-kinetic Intraparticle diffusion Elovich
Parameters k1 qe (calc) R2 k2 qe (calc) R2 Kdif C R2 β α R2 qe (exp)

Dalton Transactions Accepted Manuscript

MB 0.010 g 0.00990 19.110 0.987 1.071800 100.000 0.999 1.113 78.830 0.994 5.585 3811.010 0.980 97.470
(20 mg L-1) 0.015 g 0.00806 10.105 0.924 0.017500 67.560 0.999 0.640 55.420 0.988 3.300 386.720 0.941 66.360
0.020 g 0.00898 5.670 0.944 0.003600 50.500 0.999 0.336 44.160 0.992 1.746 130.370 0.957 49.920
SO 0.010 g 0.01280 20.860 0.952 0.000121 52.910 0.998 1.033 33.085 0.972 5.495 840.001 0.970 49.960
(10 mg L-1) 0.015 g 0.01330 14.880 0.966 0.000412 35.210 0.999 0.736 21.595 0.985 3.663 133.530 0.971 33.300
0.020 g 0.00967 7.422 0.969 0.000819 25.770 0.998 0.410 17.960 0.994 2.152 49.550 0.983 24.090
Pb2+ 0.010 g 0.00806 34.190 0.960 0.000032 158.730 0.996 2.189 116.140 0.976 11.441 7313.023 0.941 153.580
(38 mg L-1) 0.015 g 0.00944 28.170 0.979 0.000112 108.690 0.998 1.709 76.343 0.988 9.015 4848.094 0.970 104.850
0.020 g 0.00783 22.900 0.965 0.000225 87.719 0.997 1.305 61.877 0.986 6.770 4061.621 0.937 85.500
Cr3+ 0.010 g 0.00875 34.670 0.962 0.000009 208.330 0.999 1.976 170.480 0.996 10.398 6985.212 0.973 205.150
(42 mg L-1) 0.015 g 0.01080 27.580 0.950 0.000028 142.857 0.999 1.358 116.590 0.992 7.129 4383.121 0.965 139.890
0.020 g 0.01100 15.330 0.957 0.000049 106.380 0.999 0.786 91.046 0.988 4.162 1247.003 0.980 104.920
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844 Table. 5. Isotherm constant parameters and correlation coefficients calculated for the adsorption of dyes and ions onto Mn-Fe3O4-
845 NPs-AC in single component system.
Dye Ion
MB SO Cr3+ Pb2+

Dalton Transactions Accepted Manuscript

Isotherm Parameters 0.01 g 0.015 g 0.02 g 0.01 g 0.015 g 0.02 g 0.01 g 0.015g 0.02 g 0.01 g 0.015 g 0.02 g
Langmuir Qmax(mg g-1) 229.4 121.06 110.86 159.74 111.34 91.99 267.4 165.8 121.65 139.5 123.9 105.2
KL (L mg-1) 0.929 0.964 2.50 0.677 1.597 1.231 0.949 2.52 1.627 0.848 0.538 0.916
R2 0.996 0.994 0.996 0.995 0.996 0.999 0.993 0.999 0.997 0.998 0.999 0.996
RL 0.026- 0.025- 0.009- 0.036- 0.015- 0.020- 0.026- 0.009- 0.015- 0.029- 0.044- 0.027-
0.177 0.172 0.074 0.230 0.112 0.140 0.095 0.038 0.058 0.105 0.157 0.098
Freundlich 1/n 0.572 0.385 0.440 0.434 0.410 0.456 0.585 0.513 0.507 0.300 0.444 0.459
KF (L mg-1) 0.7110 5.520 6.284 5.820 5.720 5.080 8.014 7.980 6.320 6.036 5.078 5.215
R2 0.966 0.968 0.905 0.957 0.910 0.940 0.956 0.981 0.985 0.964 0.933 0.973
Temkin B1 47.173 20.606 20.62 30.07 21.09 15.78 60.91 36.07 26.34 24.63 26.91 22.71
KT(L mg-1) 10.940 19.621 37.23 9.345 22.24 18.05 8.797 25.37 16.54 14.96 5.310 9.176
R2 0.989 0.987 0.985 0.988 0.961 0.994 0.990 0.996 0.994 0.996 0.991 0.993
Dubinin- Qs (mg g-1) 134.30 86.49 80.57 109.4 84.21 66.49 182.8 125.8 87.35 115.1 90.92 77.71
radushkevich B×10-8 6.23 4.5 3.2 8.12 4.42 5.3 8.14 3.46 4.65 1.1 9.19 1.8
E (kJ mol-1) 2.833 3.333 3.952 2.500 2.481 3.071 2.478 3.801 3.279 6.742 5.270 2.333
R2 0.950 0.893 0.951 0.845 0.894 0.926 0.981 0.979 0.960 0.934 0.943 0.958
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856 Table. 6. Comparison for the removal of dyes and ions by different methods and adsorbents.
Adsorbent Dye/ion Sorption capacity Contact time Ref.
(mg g-1) (min)
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Platanus orientalis leaves powder (POLP) MB 114.94 70 63

Gold nanoparticles loaded on activated carbon MB 185.0 1.6 64
Ag nanoparticles loaded on activated carbon MB 71.43 15 65
Graphene nanosheet/magnetite (Fe3O4) composite MB 43.83 20 66

Dalton Transactions Accepted Manuscript

magnetite loaded multi-wall carbon nanotube MB 48.06 120 67
CuO-NP-AC MB 10.55 15 68
Mn-Fe3O4-NPs-AC MB 229.4 3.0 This work

Mesoporous (MCM-41) SO 68.8 120 12

Calcined Mussel Shells (CMS) SO 154.3 60 69
Fe3O4-NPs modified with SDS SO 769.2 10 70
MgO Decked Multi Layered Graphene (MDMLG) SO 137.6 120 71
NiS-NP-AC SO 53.2 5.46 30
Mn-Fe3O4-NPs-AC SO 159.7 3.0 This work

Polyacrylamide zirconium(IV) iodate Pb2+ 7.01 60 72

Olive leave powder Pb2+ 119 120 73
Enteromorpha prolifera Pb2+ 134.8 720 74
Phanerochaete chrysosporium Pb2+ 135.3 60 75
Zirconium(IV) iodosulphosalicylate Pb2+ 327.87 120 76
Mn-Fe3O4-NPs-AC Pb2+ 139.5 3.0 This work

Graphene oxide Cr3+ 92.65 120 26

Alumina nanoparticles immobilized zeolite Cr3+ 1.82 240 77
Modified Lignin Cr3+ 25 240 78
Bentonite clay Cr3+ 49.75 15 79
Activated alumina powder (AAP) Cr3+ 121.19 50 80
Mn-Fe3O4-NPs-AC Cr3+ 267.4 3.0 This work
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Dalton Transactions Accepted Manuscript

862
863 Fig. 1. UV–Vis spectra with chemical structure of MB and SO in single and quaternary solutions
864 (initial dye concentration of 10 mg L-1 for each dye and 40 mg L-1 for each ion).
865
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Dalton Transactions Accepted Manuscript

874
875 Fig. 2. (a) FE-SEM image of the prepared Mn doped Fe3O4-NPs and (b) Particle size distribution
876 of the prepared Fe3O4 particles.
877
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Dalton Transactions Accepted Manuscript

887
888 Fig. 3. (a) XRD patterns of the prepared Mn doped Fe3O4-NPs, (b) the Raman spectrum of the prepared Fe3O4 particles and (c) FT-IR
889 transmittance of the prepared Mn doped Fe3O4-NPs.

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890
891
892
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Dalton Transactions Accepted Manuscript

893
894 Fig. 4. (a) Effect of pH on the removal of MB, SO, Pb2+ and Cr3+ in the range of 2.0–10.0.
895 (General condition: adsorbent dose: 0.02 g, ultrasonic time: 4 min, in 50 mL solution, dye
896 concentration: 15 mg L-1 for each dye, ion concentration: 40 mg L-1 for each ion at room
897 temperature (25 ºC)) and (b) the experimental data versus predicted data for removal of MB, SO,
898 Pb2+ and Cr3+.
899
900
901
902
903
904
905

906
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907
908 Fig. 5. Response surfaces for the dyes removal (a) A-C (MB), (b) A-B (MB) and (c) A-D (SO).
909

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910
911 Fig. 6. Response surfaces for the ions removal (a) A-B (Cr3+), (b) A-E (Pb2+) and (c) B-F (Cr3+).

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912
913 Fig. 7. Profiles for predicated values and desirability function for removal percentage of MB,
914 SO, Pb2+ and Cr3+.
915

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Dalton Transactions

1344x401mm (72 x 72 DPI)

DOI: 10.1039/C5DT01504A
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