Synthesis of Fe3O4/Eggshell and egg membrane Nanocomposite and Application for Adsorption of Cationic and Anionic Dyes
Naereh Besharati
1
(
(Student) at Department of Chemistry, University of Guilan, Namjoo Street, Rasht, Iran.
)
nina alizadeh
2
(
Department of Chemistry, Factulty of Science, University of Guilan, Rasht, Iran
)
Keywords:
Abstract :
Synthesis of Fe3O4/Eggshell and egg membrane Nanocomposite and Application for Adsorption of Cationic and Anionic Dyes
Abstract
Keywords: Malachite green, Crystal violet, Eriochrome Black T, Egg shell and Egg membrane, Magnetic nanoparticles
INTRODUCTION
Application of bio-waste materials such as eggshell waste is strategy of using of waste materials. Low-cost eggshell waste has been widely used as a possible bone substitute, catalyst, support, and efficient bio-templates due to their high catalytic activity, ease of handling and reusability. The eggshell is an inexpensive and easily available biomaterial; it has porous structure that is related to its natural content [1-7]. Egg shells are one of the widely used food processing and manufacturing plants by-products. Eggs represent a major ingredient in a large variety of products in restaurants, whose production results in several daily tons of eggshell waste and incur considerable disposal costs in the world. About 250000 tons of eggshell waste is produced annually worldwide. Nowadays eggshell as green and economical adsorbents use for removing hydrogen sulphide and heavy metals from wastewater, so in this research MNLES and MNLEM were used for removing cationic and anionic dye. Eggshell can be widely used as a good adsorbent because of ease of handling, reusability and its low-cost waste. Many industries use dyes and pigments for coloring purposes [8]. Toxic, carcinogenic effects on humans and aesthetic effect on aquatic environment arises from dye contamination [9]. Dyes remain in the natural environment due to the persistence and non-degradation of their aromatic structure. Malachite green (MG) is a synthetic and organic compound that is use as a dye in silk, wool, jute, leather, cotton, fabric, papers and acrylic industries [10]. If it is used as a parasiticide and antibacterial chemical in fish, its residues cause carcinogenesis, mutagenesis, chromosomal fractures [11-13]. Crystal violet (CV) is a synthetic cationic dye from the triarylmethane group [14] and CV is used in black inks and for dyeing purpose such as silk, nylon, wool. It is toxic and in high value it causes eye discomfort, kidney diseases and cancer so there are interests for eliminate CV from water environment. Medically, CV is used for the treatment of burns, boils and mycotic skin infections and it has antiseptic effect on gram-positive organisms [16]. Eriochrome black-T (EBT) is used for biological coloring, dyeing silk, wool, nylon multifibers. Determination of Ca2+, Mg2+ and Zn2+ is done with complexometric method by using EBT. Dye is hazardous and its degradation product is still carcinogenic [17]. Adsorption between different methods for dye removal because of low cost, to be effective and usability is acceptable method [18, 19]. Nowadays nanotechnology develops and is used for wastewater treatment because it is affordable, trustworthy, fast and lasting [20]. Different agricultural waste materials such as palm shell [21], grape fruit peel [22], pine cone [23], pine tree leaves [24], pomelo skin based AC [25], banana pith [26], bio waste material [27], powdered waste sludge [28], wheat shells [29], palm shell powder, chitozan [30] and Coffee waste [31] are used for pollution elimination. Recent research has proven that magnetic nanoparticles, due to their unique properties act as a suitable adsorbent to remove pollutants. Intended compound and pollutants can be separate from solution with magnetic separation [32-37]. Co-precipitation is an easy method for production of Iron oxide magnetite nanoparticles (MNPs) [38-40]. So, this study focused on egg shell and egg membrane modified with magnetite nanoparticles as adsorbents for removal of MG, CV and EBT dyes and pseudo-first order, pseudo-second order, Elovich and intra-particle diffusion for kinetic models were examined. Finally, optimum conditions, Isotherm models as Langmuir, Freundlich and temkin were evaluated to obtain highest dye removal capacity.
MATERIAL AND METHODS
General
Malachite green (MG) and crystal violet (CV) as cationic dyes and eriochrome black T (EBT) as an anionic dye as shown in Fig. 1(a,b,c), Ferric chloride hexahydrate (FeCl3.6H2O), ferroussulphate heptahydrate (FeSO4.7H2O), amonia, hydrochloric acid and sodium hydroxide with the highest purity were obtained from Merck (Germany). Stock and working solutions of dyes (CCV, MG= 4 mg L-1, CEBT = 40 mg L-1) were prepared in double distilled water. show the molecular structure of CV, MG and EBT. Dye removal were done with calibration curve and improving of effective factors.
Dye adsorbtion measurements were done at λmax= 596, 620 and 530 nm, for CV, MG and EBT, respectively that were chosen as maximum absorbance wavelength from calibration curve with a spectrophotometer Jenway (model 6105, England). pH measurements were done with A Jenway pHmeter (model 370, England). The infrared spectra of Egg shell, Egg membrane, MNLES and MNLEM were sutdied in the range of 500-3500 cm-1 by a infrared instrument (FT-IR, model Alfa, Germany). Morphology of prepared samples were obtained by SEM device (model EM3200, USA). X-ray diffraction (XRD) measurement were done with philips diffractometer with mono chromatize Cu radiation (model Xpert MPD, Holland) . Egg shell and Egg membrane were crushed with Grinder (model MCG 1575, China) and stirring of solutions were done with rotator ( IKA, MS3 basic). Strong magnet 1.4 T was used for separation based on magnetic properties.
Fig. 1. Chemical structure of MG (a), CV (b), EBT (c).
Preparation of the adsorbents
Egg shell and egg membrane collected, washed and dried in oven at 105°C of, they were crushed and sieved to 150-200 μm particle size. Then the powder was dried at 105°C for 24 hours to remove moisture and stored in a closed bottle for later use in adsorption studies.
Preparation of magnetic nanoparticles loaded Egg shell and Egg membrane
Magnetite nanoparticle loaded Egg shell (MNLES) and magnetite nanoparticle loaded Egg membrane (MNLEM) were prepared by coprecipitation method. Fe2+/Fe3+ solution were prepared by dissolving FeCl3.6H2O (6.1 g) and FeSO4.7H2O (4.2 g) in 100 mL distilled water and heating to 90°C. Then 200 mL of distilled water which contains 10 mL of ammonium hydroxide (28% w/w) and 1 g of Egg shell powder and egg membrane powder (separately for prepration of MNLES and MNLEM) were added rapidly to this solution. The mixture was mixed at 80°C for 30 min while pH was regulated to 10 and then cooled to room temperature. Then Fe3O4–egg shell (MNLES) and Fe3O4–egg membrane (MNLEM) were stored after filtering, washing with distilled water, drying at 50◦C (24 h). MNLES and MNLEM adsorbents were attracted by the magnet as shown in Fig. 2 (c, f). Magnetic properties of the synthesized nanoparticles is clearly observed.
Fig. 2.(a) Pretreated Egg shell, (b) MNLES, and (c) MNLES totally attracted to magnet, (d) pretreated Egg membrane, (e) MNLEM, and (f) MNLEM totally attracted to magnet.
EDX revealed that MNLES and MNLEM have 34.57% and 20.75% Fe and 1 g egg shell and Egg membrane have 0.47 and 0.28 g Fe3O4 respectively (Fig 3).
Fig. 3.EDX of (a) MNLES and (b) MNLEM
RESULTS AND DISCUSSION
Synthesis and characterization
XRD and SEM instruments were used to emphasis on created properties of the synthesized MNLES and MNLEM. Fig. 4 shows the SEM images of MNLES and MNLEM and pretreated Egg shell, Egg membrane. Magnetite nanoparticles as shown in images, sitting on surface of egg shell and egg membrane.
Fig. 4.The SEM image of (a) pretreated egg shell, (b) MNLES, (c) pretreated egg membrane and (d) MNLEM.
The XRD pattern of MNLES and MNLEM in Fig. 5. show typical patterns of magnetite at 2θ= 30.2o, 35.6o, 43.3o and 57.2o which are corresponded with pure magnetite. The results confirm that the surfaces of egg shell and egg membrane are successfully covered with Fe3O4 nanoparticles. The average crystallite size of NPs by the Scherer equation according to the XRD pattern for MNLES was 11.5 nm and for MNLEM was 12 nm.
Fig. 5. XRD pattern of (a) Magnetite, (b) pretreated egg membrane(c) MNLEM, (d)pretreated egg shell and (e) MNLES
The FT-IR spectra of egg shell and egg membrane after and before modifieing and spectra of Fe3o4 magnetite shown in Fig. 6. The spectra display absorption bands related to magnetite nanoparticles and also different bands about Egg shell and Egg membrane.
FT-IR analysis showed –OH groups with a band at 3420 cm-1. Aliphatic C–H groups confirmed with band at 2850–2920 cm-1. The strong band at 1638–1648 cm-1 represents the C=C stretching vibrations. Absorbtion band around 1380-1415cm-1, represents S=O stretching of sulfate. The band observed at about 710 and 870cm-1 could be assigned to the alkene C=C bond. The FT-IR spectrum of MNLES and MNLA show strong band in the low-frequency region (500–1000 cm−1) due to iron oxide skeleton, which is in agreement with the magnetite spectrum. The peak at 1150 cm−1 showed the stretching bond of Fe–O and the peak at 1633 cm−1 and 3446 cm−1 implied the existence of residual hydroxyl groups. Intensity of these bonds in MNLES and MNLEM is higher than egg shell and egg membrane. It observed that there were main peak in magnetite were in MNLES and MNLEM. Thus, all the above results indicate that the magnetic nanoparticles were loaded on the Egg shell and Egg membrane.
Fig. 6. FT-IR spectra of (a) pretreated egg shell, (b) MNLES, (c) pretreated egg membrane and (d) MNLEM and(e) magnetite Fe3O4.
Dye adsorption optimization
Different parameters affecting the removal of dyes were studied to prepare maximum adsorption. Effect of different pHs on absorption of dyes were investigated with measuring absorbance of CV and MG solutions (4 mg L-1) at 596 and 620 nm, as well as EBT solution (40 mg L-1) at 530 nm. For optimization studies, suitable amount of adsorbent (MNLES or MNLEM) were added to 20mL solution of each dye at various concentrations in a 50 mL beaker and pH of the solution with HCl and NaOH (0.1 mol L-1), was regulated to the intended amount. After adsorption of dyes during proper time for mixing, spectrophotometer was used for determine residual dyes concentrations by using calibration curve after separation of adsorbents with strong magnet. This equation was used to calculate the dye removal in the experiments:
%R= 
(1)
Co and Ct are the first and remaining concentrations of the dyes after removal by synthesized adsorbents.
Effect of adsorbent amount on the dyes removal efficiency
Adsorbents amount in the range of 0.01–0.07 g (0.5-3.5 g L-1) at optimum pH in contact with 20 mL solution of 4mg L-1 of CV and MG and 40 mg L-1 of EBT were used for research on effect of adsorbent amount on dyes removal. Collision rate of dyes with adsorbents and also more accessiblity of adsorbents increase as a result of increasing the amount of adsorbents, So removal efficiency increase. The removal efficiency of MG reached maximum with 0.03 g (1.5 g L-1) of MNLES and MNLEM and for EBT reached maximum with 0.05g (2.5 g L-1) and 0.03g (1.5 g L-1) of MNLES and MNLEM, respectively. Also, the removal efficiency of CV was achieved maxium using 0.05 g (2.5 g L-1) of MNLEM. But, MNLES dosen,t have high removal efficiency for CV (Fig. 7).
Fig. 7.Effect of amount of adsorbents on the removal efficiency of CV, MG and EBT (CCV, MG =4 mg L-1, CEBT = 40 mg L-1 , V = 20 mL).
Effect of contact time on the MG, CV, EBT removal efficiency
Adsorption of dyes for review of contact time effect on the adsorption of CV and MB (4 mg L-1) and EBT (40 mg L-1) from solution were studied. Different times were used to measure absorbance of the residual solution. It was observed that 55.3 % of MG was adsorbed with MNLES after 35 min and this time is suitable for maximum removal of dye. Removal efficiency was reached to 58.7 % after 40 min. Also, MNLEM showed maximum adsorption for MG from 35 to 40 min (48.9 % to 51.9 %) (Fig. 7). Therefore 35 min was selected as a suitable time for further works. MNLEM had 53.8 to 61.6 elimination percent for CV with varing time from 40 to 60 min. Also, MNLES showed low removal efficiency as 16.4 % after 40 min and had not good adsorption for CV (Fig. 8). For EBT, the elimination percent was varied from 79.5 to 81.3 % using MNLES and during changing time from 20 to 40 min. Also, MNLEM showed 69.0 to 77.0 %removal during changing contact time from 10 to 20 min (Fig. 8).
Fig. 8. Effect of contact time on the removal efficiency of CV, MG and EBT (CCV, MG =4 mg L-1, CEBT = 40 mg L-1 , V = 20 mL).
Effect of pH on the MG , CVand EBT elimination percent
Effect of pH on removal of dyes investigated in the range of 3.0–12.0 at suitable time for mixing of solution. Fig. 9 shows the removal efficiency of dyes as a function of pH. At lower pH, surface of adsorbent has positive charge and in higher pH, surface of adsorbent has negative cherge, so anionic and cationic cantamination absorbed on it respectively. This is related to effect of pH chemistry of solution and acceptance-sites of surface. The adsorption increased by increasing solution pH and reached maximum at pH=7-12 for cationic dyes (MG and CV). For EBT as an anionic dye, the removal efficiency was increased by decreasing solution pH and reached maximum at pH=3-7.
Fig. 9. Effect of pH of solution on the CV, MG and EBT removal (CCV, MG=4 mg L-1, CEBT = 40 mg L-1 , V = 20 mL).
The study of kinetic and adsorption isotherms
The study of kinetics of CV, EBT and MG adsorption onto MNLES and MNLEM adsorbents are required for selecting optimum operating conditions for the full-scale removal processes. The kinetic parameters, which are helpful for the prediction of the adsorption rate, give important information for designing and modeling of the adsorption processes [40-43]. The kinetic data for adsorption onto MNLES and MNLEM were analyzed using pseudo-first order, pseudo-second order, Elovich and intra-particle diffusion models to find out the adsorption rate expressions. The correlation between experimental data and the kinetic models are expressed by the correlation coefficients (R2, values close to 1) and show the influence of time on the dye removal efficiency. In the present study, kinetic studies were performed in the time intervals ranged from 0 to 30 min. After contact between the adsorbents and solution of each dye (separately) during the time intervals, the clear supernatant solutions were spectrophotometrically measured for residual CV, EBT and MG concentration in the solution. Fig. (10, 11) show the equilibrium concentrations of CV and MG at the adsorption time interval of 0–30min. The concentration of residual CV, EBT and MG in the solution was monitored and the adsorption capacity at time t (qt, mg g-1) was calculated by the following equation:
(2)
where Co and Ct are the initial and equilibrium concentrations (mg L-1) of dyes at a given time t, respectively. Also, V is the solution volume (mL) and W is the weight of the adsorbent (g). The removal rate was very fast during the initial stages of the adsorption processes. The kinetic of adsorption was obtained as a pseudo-second order according to following equation. The pseudo-second order reaction rate may be dependent on the amount of solute adsorbed on the surface of adsorbent and the amount adsorbed at equilibrium. The kinetic rate equations for pseudo-second order reaction can be written as follows:
(3)
where qt and qe, are the value of adsorbed dye at each time and at equilibrium and k2 (g mg-1 min-1) is the pseudo-second order rate constant. If the second order kinetic equation is applicable, the plot of t/qt against t (Eq.(3)) should give a linear relationship. The qe and k2 can be determined from the slope and intercept of the plot. Fitting of kinetic data to pseudo-second order kinetic model, was shown in Figs. 10-12. The best fit of the pseudo-second order kinetic model (R2 close to 1) in the present system show the adsorption of MG, CV and EBT for MNLEM and EBT for MNLES followed by chemisorptions mechanism via electrostatic attraction.
Fig. 10. Fitting of kinetic data of the MG removal to the Elovich and pseudo-second order kinetic models for MNLES and MNLEM adsorbents, respectively (pH=9, adsorbent mass: 0.03 g (1.5 g L-1), CMG =3 mg L-1 for (a) MNLESand (b)MNLEM).
Fig. 11. Fitting of kinetic data of the CV to the pseudo-second order kinetic model for MNLEM (pH=9, MNLEM=0.03 g(1.5 g L-1), CCV =3 mg L-1).
Fig. 12. Fitting of kinetic data of the EBT to the pseudo-second order kinetic model (pH=4, MNLES= 0.05 g (2.5 g L-1), MNLEM= 0.03 g(1.5 g L-1), CEBT =40 mg L-1 for (a) MNLES and (b) MNLEM).
Equilibrium isotherm equations are used to describe the experimental sorption data. The parameters obtained from the different models provide important information on the sorption mechanisms and the surface properties and affinities of the sorbent. The equilibrium adsorption isotherm was determined using batch studies(Table1). 20 mL of the dye solution with various initial dyes concentrations were poured into a glass bottle. The time required to reach equilibrium as determined in equilibrium studies was 30 min. The amount of dye uptake by the MNLES and MNLEM, qe (mg g-1), was obtained by equation (2).
Adsorption data obtained in a concentration range of 10–50 mg L-1 were correlated with the following linear forms of Langmuir (Eq. (4)) [44] and Freundlich (Eq. (5)) )) [45] and Tempkin (Eq. (6)) [46].
adsorption isotherm models:
Langmuir equation:
[4]
Freundlich equation:
[5]
Tempkin equatin:
[6]
where qe is the equilibrium dyes concentration on the adsorbent (mg g-1), Ce is the equilibrium dyes concentration in the solution (mg L-1), qmax is the monolayer capacity of the adsorbent (mg g-1), KL is the Langmuir constant (L mg-1) and is related to the free energy of adsorption, KF is the Freundlich constant (L g-1) and n (dimensionless) is the heterogeneity factor.
In the Langmuir model, a plot of Ce/qe versus Ce should indicate a straight line of slope 1/qmax and an intercept of 1/ (KLqmax). K1 is related to the heat of adsorption (L g-1) and K2 is the dimensionless Tempkin isotherm.
The correlation coefficient for the adsorption isotherm study of CV (R2Langmuir=0.9642, R2Freundlich= 0.9633), EBT (R2Langmuir=0.9912, R2Freundlich=0.6727) and MG (R2Langmuir=0.9678, R2Freundlich= 0.957) (Table2) on the MNLEM adsorbent showed strong positive evidence that the adsorption of dyes follows the Langmuir isotherm. This indicates that the adsorption of dyes occurs on a homogenous surface by monolayer adsorption without any interaction between adsorbed ions. The obtained value of qmax from the Langmuir model for adsorption of CV, EBT and MG were 61.72, 21.69 and 38.31mg g -1 for MNLEM respectively.
The correlation coefficient for EBT (R2Langmuir=0.9889, R2Freundlich= 0.9909) and MG (R2Langmuir=0.8908, R2Freundlich= 0.9809) for MNLES showed that adsorption of dye onto adsorbents follows the Freundlich isotherm more than Langmuir model. The value of qmax for adsorption of EBT and MG on the MNLES was 40.0 and 25.12mg g -1, respectively.
Table 1. The values of parameters obtained by different kinetic models
Kinetic models | Parameters | MNLES | MNLEM | |||
dye | dye | |||||
EBT | MG | CV | MG | EBT | ||
Pseudo-first order | K1 ( min-1) | 1.46 | 0.014 | 0.0217 | 0.023 | 0.02 |
qe,cal (mg g -1) | 4.32 | 1.103 | 0.056 | 0.227 | 1.858 | |
R12 | 0.7219 | 0.0403 | 0.3912 | 0.058 | 0.1323 | |
Pseudo-second order | k2 (g mg-1 min-1) | 0.014 | 4.25×10-4 | 0.047 | 0.033 | 0.017 |
qe,cal (mg g -1) | 14.77 | 14.224 | 1.012 | 3.19 | 22.07 | |
R22 | 0.9955 | 0.6551 | 0.983 | 0.982 | 0.9988 | |
Elovich | ß | 0.35 | 0.616 | 4.06 | 25.83 | 0.306 |
α | 8.88 | 12.11 | 0.091 | 1.7×1023 | 58.82 | |
R2 | 0.921 | 0.9933 | 0.9547 | 0.979 | 0.8493 | |
Table 2. The constants values of different adsorption models.
Isotherm models |
Parameters | Adsorbent | ||||||
MNLES | MNLEM | |||||||
Dye | Dye | |||||||
EBT | MG | CV | MG | EBT | ||||
Langmuir | qmax (mg g-1) | 40 | 25.12 | 61.72 | 38.31 | 21.69 | ||
R2 | 0.9889 | 0.8908 | 0.9642 | 0.9678 | 0.9912 | |||
KL (L mg-1) | 0.04 | 0.12 | -0.736 | -0.42 | 7.81 | |||
Freundlich | KF | 2.07 | 156.31 | 600.48 | 1.9×103 | 18.31 | ||
n | 1.34 | 1.35 | -3.61 | -0.54 | 14.53 | |||
R2 | 0.9909 | 0.9809 | 0.9633 | 0.957 | 0.6727 | |||
Temkin | K1 | 6.9061 | 1819 | -0.27 | -373.03 | 1.234 | ||
R2 | 0.9683 | 0.7402 | 0.806 | 0.7623 | 0.6502 | |||
K2 | 0.67 | 1.024 | 0.139 | 0.138 | 3.72×106 | |||
CONCLUSION
The sorption of pollutants from aqueous solutions plays a significant role in water pollution control. The MNLES and MNLEM are synthesized easily. Due to their very high surface areas, high adsorption capacity can be achieved using magnetic nanoparticles loaded them. For this purpose, the utilization of the MNLES and MNLEM as efficient adsorbents were successfully carried out for removal of MG, EBT, CV. XRD pattern of MNLES and MNLEM were corresponded to pure magnetite at 2θ= 30.2o, 35.6o, 43.3o and 57.2o. FTIR showed that main peak in 580, 1620 and 3407cm-1 in MNLES and MNLEM similar magnetite. SEM pictures showed that nanoparticles loaded on natural adsorbents in nm size. XRD pattern of MNLES and MNLEM were corresponded to pure magnetite at 2θ= 30.2o, 35.6o, 43.3o and 57.2o. EDX revealed that MNLES and MNLEM have 34.57% and 20.75% Fe and 1 g Egg shell and Egg membrane have 0.47 and 0.28 g Fe3O4 respectively. The results confirm that the surfaces of egg shell and egg membrane are successfully covered with Fe3O4 nanoparticles. The adsorption followed the pseudo-second order kinetic model, suggesting chemisorption mechanism. The fit of the Langmuir model on the adsorption data of MNLEM for CV(R2Langmuir=0.9642), EBT(R2Langmuir=0.9912) and MG (R2Langmuir=0.9678) in the present system shows the formation of a monolayer covering of the adsorbate at the outer space of the adsorbent. The obtained value of qmax from the Langmuir model for adsorption of CV, EBT and MG were 61.72, 21.69 and 38.31mg g -1 for MNLEM respectively. For MNLES adsorption data of MG and MG (R2Freundlich= 0.9809)and EBT(R2Freundlich= 0.9909) were fitted well to the Freundlich model. The value of qmax for adsorption of EBT and MG on the MNLES was 40.0 and 25.12mg g -1, respectively. The data reported here should be useful for the design and fabrication of an economically treatment process for dye adsorption in industrial effluents.
ACKNOWLEDGMENT
Authors acknowledge financial support from Reseach Consil of University of Guilan.
CONFLICT OF INTEREST
The authors declare that there is no conflict of interests regarding the publication of this
manuscript.
REFERENCES
1. WJ. Stadelman, Eggs and egg products. Encyclopedia of Food Science and Technology; Wiley and sons, Newyork (2000).
2. NY. Mezenner, A. Bensmaili, Chem. Engin. J., 147, 87–96 (2009).
3. Z. Wei, C. Xu, B. Li, Bioresour Technol., 100, 2883–5 (2009).
4. S. Yoo JS. Hsieh, P. Zou, J. Kokoszka, Bioresource Technology., 100, 6416–21 (2009).
5. WH. Eisa, YK. Abdel-Moneam, Y. Shaaban, AA. Abdel-Fattah, AMA. Zeid, Mater Chem Phys., 128, 109–13 (2011).
6. T-X. Fan, S-K Chow, D. Zhang, Prog Mater Sci., 54, 542–659 (2009).
7. W. Zhang, D. Zhang, T. Fan J. Gu, J. Ding, H. Wang, et al, Chem Mater., 21, 33–40 (2008).
8. AA. Ghani, R. Santiagoo, AC. Johnson, N. Ibrahim, S. Selamat., IcoSM (2007).
9. PS. Ratna, PS. Padhi, Pollution Due to Synthetic Dyes Toxicity & Carcinogenicity Studies and Remediation. Int. Env. Science., 3, 940 – 955 (2012).
10. S. Srivastava, R. Sinha, D. Roya, Aquatic Toxicology., 66, 319–329 (2004).
11. Food standards Australia newzeland, Malachite green in aquacultured fish. http://www.foodstandards.gov.au/consumer/chemicals/malachitegreen/Pages/default.aspx
12. R. Mirzajani, S. Ahmadi, Indust. Engin. Chem., 23, 171-178 (2015).
13. S. Namrodi, M. Golipor, H. Mirrezai, M. Mazandarani, National conference about planning of environmental protection (2013).
14. G. Alsenani, J. Amer. Scien., 9, 30-35 (2013).
15. LK. Akinola, AM. Umar, J. Appl. Sci. Environ. Manage., 19, 279 – 288 (2015).
16. F. Moeinpour, A. Alimoradi, M. Kazemi, J. Envir. Health. Sci. Eng., 12, 112 (2014).
17. ND. Pragnesh, K. Satinder, K. Ecta, J. Chem.ech., 18, 53-60 (2011).
18. NN. Nasssar, NM. Marei, G. Vitale, LA. Arar, Chem. Engin. 93 (2015).
19. Kanchi. Suvardhan, Environ. Anal. Chem (2014).
20. G. Sreelatha, V. Ageetha, J. Parmer, P. Padmaja, J. Chem. Engin. Data., 56, 35-42 (2010).
21. M. Torab-Mostaedi, M. Asadollahzadeh, A. Hemmati , A. Khosravi, J. Taiwan Inst. Chem. Eng., 44, 295-302 (2013).
22. NM. Mahmoodi, B. Hayati, M. arami, C. Lan, Adsorption of textile dyes on Pine cone from colored wastewater: Kinetic, equilibrium and thermodynamic studies. Desalination., 268, 117-125 (2010).
23. F. Deniz, S. Karaman, Chem. Eng. J., 170, 67-74 (2011).
24 CA. Almeide, NA. Debacher, AJ. Downs, L. Cottet, CA. Mello, J. Colloid interface SCI., 332, 46-53 (2009).
25. C. Namasivayam, N. Kanchana, Chemosphere., 25, 1691–1706 (1992).
26. S. Kaur, S. Rani, RK. Mahajan, J. Chem (2011).
27. O. Serpil, K. Fikret, Environ. Manage., 81, 307–314 (2006).
28. Y. Bulut, N. Gozubenli, H. Aydin, Hazard. Mater., 144, 300–306 (2007).
29. G. Sreelatha, V. Ageetha, J. Parmar, P. Padmaja, G. Chem. Eng., 56, 35-42 (2014).
30. R. Lafi, AB. Fradj, A. Haiane, BH. Hameed, Korean. J. Chem. Eng., 1-9 (2014).
31. F. Ovaisi, M. Nikazar, MH. Razagi, National conference about planning of environmental protection (2012).
32. W. WU, Q. He, C. Jiang, Nanoscale Res Lett., 33, 97–415 (2008).
33. F. Bandari, F. Safa, SH. Shariati, Science. Engin., 40, 3363-3372 (2015).
34. M. Golshekan, SH. Shariati, Acta. Chim. Slov., 60, 358-367 (2013).
35. M. Manoochehri, SM. Mostashari, Shariatim S.H, Cell. Chem. Tech., 47, 727-734 (2013).
36. SH. Shariati, M. Faraji, Y. Yamini, AA. Rajabi, Else. Desal., 270, 160-165 (2011).
37. N. Yang, S. Zhu, D. Zhang, S. Xu, Mater. Lett., 62, 645–647 (2008).
38. J. Park, K. An, Y. Hwang, JG. Park, HJ. Noh, JY. Kim, JH. Park, NM. Hwang, T. Hyeon, Nat. Mater., 3, 891–895 (2004).
39. JH. Jang, HB. Lim, Microchem., 94, 148–158 (2010).
40. S. Ahmadi, A. Rahdar, S. Rahdar, C.A. Igwegbe, Desalination and water treatment, 152, 401-410 (2019).
41. A. Rahdara, S. Ahmadi, J. Fu, S. Rahdar, Desalination and water treatment., 137, 174-182 (2019).
42. S. Rahdar, A. Rahdar, C.A. Igwegbe, F. Moghaddam, S. Ahmadi, Desalination and water treatment., 141, 386-393 (2019).
43. A. M.Khan, F. Shafiq, S. A. Khan, S. Ali, B. Ismail, A. S. Hakeem, A. Rahdar, M. F. Nazar, M. Sayed, A. R. Khana, J. molecular liquids., 274, 673-680 (2019).
44. I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum. Am. Chem. Soc., 40, 1361–1403 (1918).
45. HMF. Freundlich, Over the adsorption in solution. Z. Phys. Chem., 57, 385–470 (1906).
46. MJ. Tempkin, V. Pyzhev, Recent modifications to langmuir isotherms. Acta Physiol. Chem. USSR., 12, 271(1940).
Symbols:
MNLES: Magnetite nanoparticles loaded green egg shell.
MNLEM: Magnetite nanoparticles loaded egg membrane.
qe: equilibrium dye concentration on the adsorbent.
Ce: equilibrium dye concentration in the solution.
qmax: monolayer capacity of the adsorbent.
KL: Langmuir constant.
KF: Freundlich constant.
N: Degree of nonlinearity of adsorption.
