Artificial Neural Network Optimization of Adsorption Parameters for Cr(VI), Ni(II) and Cu(II) Ions Removal from Aqueous Solutions by Riverbed Sand

Document Type : Research Article


1 Department of Chemistry, C.P.A.College, Bodinayakanur

2 Regional Joint Director of Collegiate Education, Triunelveli Region, Tirunelveli.



Removal of Cr(VI), Ni(II), and Cu(II) from aqueous solution by Riverbed Sand containing Quartz as major clay minerals as a non-toxic and economically viable treatment was investigated. The structure, morphology, surface area, and elemental composition were confirmed using XRD, SEM, EDAX, FT-IR, and BET techniques. The N2 adsorption-desorption isotherm reveals their mesoporous structure and large BET surface area (122.75 m²/g). The effect of the initial metal concentration, pH, adsorption dosage, contact time, and temperature were examined in batch experiments to understand adsorption isotherms, kinetics, and thermodynamics. Results suggest that the equilibrium adsorption was described by the Langmuir model. Adsorption kinetics was described well by the pseudo-second-order model and were followed by an intraparticle diffusion mechanism. The thermodynamics studies reveal that the adsorption was spontaneous and exothermic. An Artificial Neural Network (ANN) model was used to optimize the removal efficiency of Cr(VI), Ni(II), and Cu(II) on QKCI. The model was developed using a three-layer feed-forward backpropagation algorithm with 15, 18, and 20 hidden neurons for Cr(VI), Ni(II), and Cu(II) ions. Comparison between the model results and experimental data gives a high degree of correlation (R2= 0.9863 for Cr(VI), 0.9591 for Cu(II)) and 0.9469 for Ni(II) indicating that the model is able to predict the sorption efficiency with reasonable accuracy.


Main Subjects

[1] Ghosh A., Pal M., Biswas K., Ghosh U.C., Manna B., Manganese Oxide Incorporated Ferric Oxide Nanocomposites (MIFN): a Novel Adsorbent for Effective Removal of Cr (VI) from Contaminated Water, J. Water Process Eng., 7: 176-186 (2015).
[3] Wu F.C., Tseng R.L., Juang R.S., Kinetic Modeling of Liquid-Phase Adsorption of Reactive Dyes and
Metal Ions on Chitosan.
Water Res., 35: 613-618 (2001).
[6] Wang X., Lou Y., Ye X., Chena X., Fang L., Zhai Y., Zheng Y., Xiong C.,  Green Chemical Method
for the Synthesis of Chromogenic Fiber and its Application for the Detection and Extraction of Hg2+ And Cu2+ in Environmental Medium
, J. Hazard. Mater., 364: 339–348(2019).
[7] Qiu J., Wang Z., Li H., Ling X., Jing P., Zhai M., Adsorption of Cr(VI) Using Silica-Based Adsorbent Prepared by Radiation-Induced Grafting, J. Hazard. Mater., 166: 270–276 (2009). 
[8] EI-Shafey E.I., Cox M., Pichigin A.A., Appleton Q., Application of a Carbon Sorbent for the Removal
of Cadmium and other Heavy Metal Ions from Aqueous Solution,
J. Chem. Technol. Biotechnol. 77(4): 429-436 (2002).
[10] Langeroodi N.S., Safaei E., Investigation of Removal of Cu (II) Ions by Commercial Activated Carbon: Equilibrium and Thermodynamic Studies,  Prot. Met. Phys. Chem. Surf., 55 (1): 28-33 (2019).
[11] Bhattacharya K.G., Gupta S.S., Adsorptive Accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from Water on Montmorillonite: Influence of Acid Activation, J. Colloid. Interface Sci., 310: 411-424 (2007).
[13] Zhou S., Xue A., Zhang Y., Li M., Li K., Zhao Y., Xing W., Novel Polyamidoamine Dendrimer-Functionalized Palygorskite Adsorbents with High Adsorption Capacity for Pb2 + and Reactive Dyes,  Appl. Clay Sci., 107: 220-229 (2015).
[14] Lata H., Garg V.K., Gupta R. K., Sequestration of Nickel from Aqueous Solution onto Activated Carbon Prepared From Parthenium Hysterophorus L. J. Hazard. Mater., 157: 503-509 (2008).
[15] Amuda O.S., Giwa A. A., Bello I. A., Removal of Heavy Metal from Industrial Wastewater Using Modified Activated Coconut Shell Carbon, Biochem. Eng. J., 36: 174-181 (2007).
[16] Tirtom V. K., Dinçer A., Decerik S., Ayudemir T., Celik A., Comparative Adsorption of Ni(II) and Cd(II) Ions on Epichlorohydrin Crosslinked Chitosan–Clay Composite Beads in Aqueous Solution, Chem. Eng. J., 197: 379-386 (2012).
[17] Nayak P.S., Singh B.K., Instrumental Characterization of Clay by XRF, XRD and FTIR, Bull. Mater. Sci., 30(3): 235–238 (2007).
[18] Grim R. E, “Clay Miner.”, Mcgraw-Hill Book Co. New York, (1968).
[19] Sarala Thambavani D., Kavitha B., Prediction and Simulation of Chromium (VI) Ions Removal Efficiency by Riverbed Sand Adsorbent Using Artificial Neural Networks, Int. J. Eng. Sci. Res. Tech., 3: 906-913 (2014).
[21] Kavitha B., Saralathambavani D., Adsorption of Chromium (VI) Ions by Riverbed Sand from Mullai Periyar, Tamilnadu, Chem. Sci. Rev. Lett., 3: 847-859 (2014).
[23] Assefi A., Ghaedi M., Ansari A., Hibibi M. H., Momeni M. S., Removal of Malachite Green From Aqueous Solution by Zinc Oxide Nanoparticle Loaded on Activated Carbon: Kinetics and Isotherm StudyJ. Ind. Eng. Chem., 20: 2905-2913 (2014).
[25] Khataee A. R., Zarei M., Dehghan G., Ebadi E., Powhassan M., Biotreatment of a Triphenylmethane Dye Solution Using a Xanthophyta Alga: Modeling of Key Factors By Neural Network, J. Taiwan Inst. Chem. Eng., 42: 380-386 (2011).
[26] Khataee A., Khani A., A Neural Network Approach For Prediction of Main Product Yields in Methanol
to Olefins Process,
Int. J. Chem. React. Eng., 7: 1542-6580 (2009).
[27] Khataee A.R., Fathinia M., Zarei M., Izadkhah  B., Joo S.W., Modeling and Optimization of Photocatalytic/Photoassisted-Electro-Fenton Like Degradation of Phenol Using a Neural Network Coupled with Genetic Algorithm, J. Ind. Eng. Chem, 20(4): 1852-1860 (2014).
[30] Jamshidi M., Ghaedi M., Dashtian K., Ghaedi A.M., Hajati S., Goudarzi A., Highly Efficient Simultaneous Ultrasonic Assisted Adsorption of Brilliant Green and Eosin B onto Zns Nanoparticles Loaded Activated Carbon: Artificial Neural Network Modeling, Spectrochim Acta A., 153: 257-267 (2016).
[31] Kiransan M., Khataee A., Karaca S., Sheydaei M., Artificial Neural Network Modeling of Photocatalytic Removal of o Disperse Dye Using Synthesized of ZnO Nanoparticles on Montmorillonite, Spectrochim. Acta, Part-A., 140: 465-473 (2015).
[32] Rene E. R., Veiga M. C., Kennes C., Experimental and Neural Model Analysis of Styrene Removal From Polluted Air in a Biofilter, J. Chem. Techol. Biotechnol. 84: 941-948 (2009).
[33] Elías A., Ibarra-Berastegi G., Arias R., Barona A., Neural Networks as a Tool for Control and Management of a Biological Reactor for Treating Hydrogen Sulphide, Bioprocess. Biosyst. Eng., 29: 129-136 (2006).
[34] Movagharnejad K., Nikzad M., Modeling of Tomato Drying Using Artificial Neural Network, Comput. Elect. Agri., 59: 78-85 (2007).
[35] Sadrzadeh M., Mohammadi T., Ivakpour J., Kasiri N., Separation of Lead Ions from Wastewater Using Electrodialysis: Comparing Mathematical and Neural Network Modeling, Chem. Eng. J., 144: 431-441 (2008).
[36] Van Der Marel H.M., Beutelspacher H., Atlas of IR Spectroscopy of Clay Minerals Their Admixtures, CNY. Elsevier Science Publication, (1976).
[37] Tuddenham W.M., Lyon R.J.P., Infrared Techniques in the Identification and Measurement of Minerals, Anal. Chem., 32:1630-1634 (1960).
[38] Gadsen J.A., 1975, Infrared Spectra of Minerals and Related Inorganic Compounds (London: Butler Works)
[40] Guyo U., Makawa T., Moyo M., Nharingo T., Nyamunda B.C., Mugadza T., Application of Response Surface Methodology for Cd(II) Adsorption on Maize Tassel-Magnetite Nanohybrid Adsorbent, Journal of Environmental Chemical Engineering, 3(4): 2472-2483 (2015)
[41] Runtti H., Tuomikoski S., Kangas T., Lassi U., Kuokkanen T., Rämö J., Chemically Activated Carbon Residue from Biomass Gasification as a Sorbent for Iron (II), Copper (II) and Nickel (II) Ions, J.  Water Process Eng., 4: 12–24 (2014).
[42] Singh P.N., Tiwary D., Sinha I., Improved Removal of Cr (VI) by Starch Functionalized Iron Oxide Nanoparticles, J. Environ. Chem. Eng., 2: 2252–2258 (2014).
[44] Mittal A., Mittal J., Malviaya A., Gupta V. K., Adsorptive Removal of Hazardous Anionic Dye "Congo Red" from Wastewater Using Waste Materials and Recovery By Desorption, J. Colloid Interface Sci. 340: 16-26 (2009).
[45] Zhang Z., Shan Y., Wang J., Ling H., Zang S., Gao W., Zhao Z., Zhang H., Investigation on the Rapid Degradation of Congo Red Catalyzed /by Activated Carbon Powder Under Microwave Irradiation, J. Hazard. Mater., 147: 325-333 (2007).
[46] Nasernejad B., Zadeh T., Pour B. B., Bygi M. E., Zamani A., Comparison for Biosorption Modeling
of Heavy Metals (Cr (III), Cu (II), Zn (II)) Adsorption from Wastewater by Carrot Residues,
Process Biochem., 40: 1319–1322 (2005).
[47] Gupta V. K., Agarwal S., Saleh T.A., Chromium Removal By Combining The Magnetic Properties of Iron Oxide with Adsorption Properties of Carbon Nanotubes, Water Res., 45: 2207-2212 (2011).
[48] Mane S.M., Vanjara A.K., Sawant M.K., Removal of Phenol from Wastewater Using Date Seed Carbon,
J. Chin. Chem. Soc., 52:1117-1122 (2005).
[49] Monier M., Ayad D.M., Wei Y., Sarhan A.A., Adsorption of Cu(II), Co(II), And Ni(II) Ions
by Modified Magnetic Chitosan Chelating Resin,
J. Hazard. Mater., 177: 962–970 (2010).
[50] Langmuir I., The Adsorption of Gases on Plane Surfaces of Glass, Mica And Platinum, J. Am. Chem. Soc., 40:1361-1430 (1918).
[51] Langeroodi N.S., Farhadravesh Z,  Khalaji A.D., Optimization of Adsorption Parameters for Fe (III) Ions Removal from Aqueous Solutions by Transition Metal Oxide Nanocomposite, Green Chem. Let. Rev., 11(4): 404-413 (2018).
[52] Nasehi S. M., Ansari S., Sarshar M., Removal of Dark Colored Compounds from Date Syrup Using Activated Carbon: a Kinetic Study, J. Food Eng., 111: 490-495 (2012).
[53] Mittal A., Malviya A., Kaur D., Mittal J., Kurup L., Studies on The Adsorption Kinetics and Isotherms for The Removal and Recovery of Methyl Orange from Wastewaters Using Waste Materials, J. Hazard. Mater., 148:229-240 (2007).
[56] Purkait M.K., Gusain D.S., Das Gupta S., De S.,Adsorption Behavior of Chrysoidine Dye on Activated Charcoal and its Regeneration Characteristics by Using Different Surfactants, Sep. Sci. Technol. 39(10): 2419 – 2440(2005).
[57] Ho Y.S., Mckay G., Pseudo-Second order Model for Sorption Processes, Process Biochem., 34: 451-465 (1999).
[58] Mirania S., Langeroodi N.S., Goudarzi A., Ebrahimi P., Mn2+ Ions Retention onto Agriculture Waste:
A Statistical Design Analysis, Estimation of Equilibrium and Kinetic Parameters,
Desalin Water Treat., 72:52-60 (2017).
[59] Weber Jr., W.J., Morris, J.C., Sanit, J., Kinetics of Adsorption on Carbon from Solution, Journal of The Sanitary Engineering Division, American Society of Civil Engineers, 89:31-60 (1963).
[60] Li W., Tang Y., Zeng Y., Tong Z., Liang D., Cui W., Adsorption Behavior of Cr(VI) Ions on Tannin-Immobilized Activated Clay, Chem. Eng. J., 193-194: 88–95 (2012).
[61] Weng C.H., Sharma Y.C., Chu S.H., Adsorption of Cr(VI) from Aqueous Solutions by Spent Activated Clay, J. Hazard. Mater. 155:65–75 (2008).
[63] Yuan P., Fan M., Yang D., He H., Liu D., Yuan A., Zhu J.X., Chen T.H., Montmorillonite-Supported Magnetite Nanoparticles for the Removal of Hexavalent Chromium [Cr(VI)] from Aqueous Solutions, J. Hazard. Mater. 166:821–829 (2009).
[64] Krishna B.S., Murty D.S.R., Jai Prakash B.S., Surfactant-Modified Clay as Adsorbent for Chromate, Appl. Clay Sci., 20:65–71 (2001).
[65] Yadav S., Srivastava V., Banerjee S., Weng C.H., Sharma Y.C., Adsorption Characteristics of Modified Sand for the Removal of Hexavalent Chromium Ions from Aqueous Solutions: Kinetic, Thermodynamic and Equilibrium Studies, Catena, 100: 120–127 (2012).
[66] Sharma Y.C., Uma, Srivastava V., Srivastava J., Mahto M., Reclamation of Cr(VI) Rich Water
and Wastewater by Wollastonite,
Chem. Eng. J., 127: 151–156 (2007).
[67] Yadav S., Srivastava V., Banerjee S., Gode F., Sharma Y. C., Studies on the Removal of Nickel from Aqueous Solutions Using Modified Riverbed Sand, Environ. Sci. Pollut. Res.,  20: 558–567 (2013).
[68] Assefi P., Ghaedi M., Ansari A., Hibibi M.H., Momeni M.S., Artificial Neural Network Optimization for Removal of Hazardous Dye Eosin Y from Aqueous Solution Using Co2O3-NP-AC: Isotherm and Kinetics Study, J. Ind. Eng. Chem. 20: 2905-2913 (2014).