Document Type : Original Article


Department of Civil Engineering, Sirjan University of Technology, Sirjan, Iran


In recent years, zero-valent iron has drawn a great attention in wastewater treatment and ground water remediation. It can effectively remove priority water contaminants, but there are some disadvantages in the use of nZVI particles, such as high tendency to agglomerate, lack of stability, secondary iron pollution, separation and recovery of the fine nZVI particles after utilization. Using supporting material for nZVI is a promising way to solve these problems. Clay minerals as abundant natural resources are appropriate candidates to act as supporting materials. In this study, the use of fibrous clays-supported nZVI composite for the remediation of contaminated aqueous solutions will be discussed.
 Materials and methods:
Sepiolite and Palygorskite- nano zero valent iron composites were made using green tea extract. In order to determine sorption capacity of nZVI - sepiolite and palygorskite composites for phosphorous, cadmium and nickle based on isotherm models, different concentrations of these ions were equilibrated with the composites in 1% suspensions for 24 h. After adsorption, the supernatant liquids were filtered and the residual pollutants concentrations were determined. 
Results and discussion:
Results showed that Langmuir and Freundlich models were the best models describing p sorption on both composites. The estimated maximum adsorption capacity of the Sep-nZVI and Pal-nZVI using the Langmuir model (qmax) was 11.38 mg P/g and 8.57 mg P/g . The cadmium  adsorption data of both sorbents best fitted to the Langmuir, Fruendlich and dubinin–radushkevich models. Results clearly demonstrateD the much higher Cd sorption potential of sepiolite compared to palygorskite. Sorption capacities (qmax) of Sepiolite- nZVI and palygorskite nZVI composite for Ni were 11.14 and 32.3 mgr/gr, respectively. The Ni sorption affinity (KL) of palygorskite nZVI was also greater than that of Sepiolite- nZVI. The favorability of a sorption system can be predicted by the constant separation factor RL. In the current study, RL values for palygorskite nZVI and Sepiolite- nZVI were greater than zero and less than unity indicating favorable sorption of P, Cd and Ni onto the two composites. 
Fibrous clays – nano zero valent iron can be used as efficient sorbents for phosphorus removal from urban wastewater and removal of cadmium and nickle from industrial wastewater due to their friendly environmental nature and high performance toward pollutants removal.


  1. Al-Rashdi, B.A.M., Johnson, D.J. and Hilal, N., 2013. Removal of heavy metal ions by nanofiltration. Desalination. 315, 2-17.
  2. Bhowmick, S., Chakraborty, S., Mondal, P., Van Renterghem, W., Van den Berghe, S., Roman-Ross, G., Chatterjee, D. and Iglesias, M., 2014. Montmorillonite-supported nanoscale zero-valent iron for removal of arsenic from aqueous solution: kinetics and mechanism, Chemical Engineering Journal. 243, 14–23.
  3. Boparai, H. K., Joseph, M., and O’Carroll, D. M., 2013. Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling. Environmental Science and Pollution Research. 20, 6210-6221.
  4. Chipera, S. and Bisch. D. L., 2001. Baseline studies of the Clay Minerals Society Source Clays: powder X-ray diffraction analysis. Clay and Clay Minerals. 49, 398-409.
  5. Duru, I., Ege, D., Kamali, A.R., 2016. Graphene oxides for removal of heavy and precious metals from wastewater, Journal of Materials Science. 51, 6097–6116.
  6. Essington, M. E. 2004. Soil and Water Chemistry: An Interrative Approach. CRC Press, Boca Raton, Florida.
  7. Giasuddin A.B.M., Kanel, S.R. and Choi, H., 2007. Adsorption of humic acid onto nanoscale zerovalent iron and its effect on arsenic removal. Environmental Science Technology. 41, 2022–2027.
  8. Giels, C. H., Silva, A. P. D. and Easton. I. A., 1974. A general treatment and classification of the solute adsorption isotherm. part. II. Experimental interpretation. Journal of Colloid and Interface Science. 47, 766-778.
  9. Hua, M., Zhang, Sh., Pan, b., Zhang, w., Lv, L. and Zhang, Q., 2012. Heavy metal removal from water/wastewater by nanosized metal oxides: A review. Journal of Hazardous Materials. 211– 212, 317-331.
  10. Karn, B., Kuiken, T., Otto, M., 2009. Nanotechnology and in situ remediation: a review of the benefits and potential risks. Environmental health perspectives, 117, 1813-1831.
  11. Krastanov, A., Alexieva, Z. and Yemendzhiev, H., 2013. Microbial degradation of phenol and phenolic derivatives, Engineering of Life Science. 13, 76–87.
  12. Li, Y., Li, J. and Zhang, Y., 2012. Mechanism insights into enhanced Cr (VI) removal using nanoscale zerovalent iron supported on the pillared bentonite by macroscopic and spectroscopic studies, Journal of Hazardous materials. 227, 211–218.
  13. Li, Z., Dong, H., Zhang, Y., Li, J. and Li, Y., 2017. Enhanced removal of Ni(II) by nanoscale zero valent iron supported on Nasaturated bentonite. Journal of Colloid and Interface Science. doi: http://
  14. Li, Z., Zongwei Ma, Z., Jan van der Kuijp, J., Yuan, Z. and Huang, L., 2014. A reviewof soil heavymetal pollution frommines in China: Pollution and health risk assessment. Science of the Total Environment. 468–469, 843–853.
  15. Lin, S. H. and Juang, R. S., 2002. Heavy metal removal from water by sorption using surfactant-modified montmorillonite. Journal of Hazardous Materials. B92, 315-326.
  16. Millar, G.J., Couperthwaite, S.J. and Papworth, S., 2016. Ion exchange of sodium chloride and sodium bicarbonate solutions using strong acid cation resins in relation to coal seam water treatment, Journal of Water Process Engineering. 11, 60–67.
  17. Millar, G.J., Couperthwaite, S.J., de Bruyn, M. and Leung, C.W., 2015. Ion exchange treatment of saline solutions using Lanxess S108H strong acid cation resin, Chemical Engineering Journal. 280, 525–535.
  18. Millar, G.J., Lin, J., Arshad, A., Couperthwaite, S.J., 2014. Evaluation of electrocoagulation for the pre-treatment of coal seam water, Journal of Water Process Engineering. 4, 166–178.
  19. Pang, Z.H., Liu, Y., Luo, J. and Lei, Y.T., 2013. Influence factors on removal of cadmium by montmorillonite supported nano zero-valent iron, Advanced Materials Research. 807, 539–542.
  20. Qiu, X., Fang, Z., Yan, X., F. and Gu, F., 2012. Emergency remediation of simulated chromium (VI)-polluted river by nanoscale zero-valent iron: laboratory study and numerical simulation, Chemical Engineering Journal.193, 358–365.
  21. Qu, X., Alvarez, P.J.J. and Li, Q., 2013. Applications of nanotechnology in water and wastewater treatment, Water Resource. 47, 3931–3946.
  22. Sheikhhosseini, A., Shirvani, M., Shariatmadari, H., Zvomuya, F. and Najafic, B., 2014. Kinetics and thermodynamics of nickel sorption to calcium–palygorskite and calcium–sepiolite: A batch study. Geoderma. 217–218, 111–117.
  23. Shi, L. N., Zhou, Y., Chen, Z., Megharaj, M. and Naidu, R., 2013. Simultaneous adsorption and degradation of Zn2+ and Cu2+ from wastewaters using nanoscale zerovalent iron impregnated with clays, Environmental Science and Pollution Research. 20, 3639– 3648.
  24. Shirvani, M., Shariatmadari, H., Kalbasi, M., Nourbakhsh, F. and Najafi, B. 2006. Sorption of cadmium on palygorskite, sepiolite and calcite: Equilibria and organic ligand affected kinetics.
  25. Colloids and Surfaces A: Physicochemical Engineering Aspects. 287, 182–190.
  26. Simate, G.S., Maledi, N., Ochieng, A., Ndlovu, S., Zhang, J. and Walubita, L.F., 2016. Coalbased adsorbents for water and wastewater treatment, Journal of Environmental Chemical Engineering. 4, 2291–2312.
  27. Soliemanzadeh, A., Fekri, M. 2017a. Synthesis of clay-supported nanoscale zero-valent iron using green tea extract for the removal of phosphorus from aqueous solutions. Chinese Journal of Chemical Engineering, DOI: 10.1016/j.cjche.2016.12.006.
  28. Soliemanzadeh, A., Fekri, M., 2017b. The application of green tea extract to prepare bentonite-supported nanoscale zero-valent iron and its performance on removal of Cr(VI): Effect of relative parameters and soil experiments, Microporous and Mesoporous Materials. 239, 60-69.
  29. Soliemanzadeh, A., Fekri, M., Bakhtiary , S., Mehrizi, M.H., 2016. Biosynthesis of iron nanoparticles and their application in removing phosphorus from aqueous solutions. Chemistry and Ecology. 32, 286-300.
  30. Stumm, W., and Morgan, J. J., 2012. Aquatic chemistry: chemical equilibria and rates in natural waters. Vol. 126. John Wiley and Sons.
  31. Tandon, P.K., Shukla, R.C., Singh, S.B., 2013. Removal of arsenic (III) from water with clay-supported zerovalent iron nanoparticles synthesized with the help of tea liquor. Industrial & Engineering Chemistry Research. 52, 10052-10058.
  32. Teh, C.Y., Budiman, P.M., Shak, K.P.Y. and Wu, T.Y., 2016. Recent advancement of coagulation-flocculation and its application in wastewater treatment, Industrial & Engineering Chemistry Research. 55, 4363–4389.
  33. Tomar, V., Prasad, S., Kumar, D., 2014. Adsorptive removal of fluoride from aqueous media using Citrus limonum (lemon) leaf. Microchemical Journal. 112, 97-103.
  34. Üzüm, Ç., Shahwan, T., Eroğlu, A.E., Hallam, K.R., Scott, T.B., Lieberwirth, I., 2009. Synthesis and characterization of kaolinite-supported zero-valent iron nanoparticles and their application for the removal of aqueous Cu 2+ and Co 2+ ions. Applied Clay Science. 43, 172-181.
  35. Viseras C. and Lopez-Galindo. A., 1999. Pharmaceutical applications of some Spanish clays (sepiolite, palygorskite, bentonite): some preformulation studies. Applied Clay Science. 14, 69-82.
  36. Wang, J., Liu, G., Zhou, C., Li, T., and Liu, J., 2014. Synthesis, characterization and aging study of kaolinite-supported zero-valent iron nanoparticles and its application for Ni(II) adsorption, Materials Research Bulletin. 60, 421–432.
  37. Wang, Z., Nie, E., Li, J., Yang, M., Zhao, Y., Luo, X. and Zheng, Z., 2012. Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon. Environmental Science and Pollution Research 19, 2908-2917.
  38. Xi, Y., Megharaj, M. and Naidu, R., 2011. Dispersion of zerovalent iron nanoparticles onto bentonites and use of these catalysts for orange II decolourisation, Applied Clay Science. 53, 716–722.
  39. Xi, Y., Sun, Z., Hreid, T., Ayoko, G.A. and Frost, R.L., 2014. Bisphenol A degradation enhanced by air bubbles via advanced oxidation using in situ generated ferrous ions from nano zero-valent iron/palygorskite composite materials, Chemical Engineering Journal. 247, 66–74.
  40. Yan, L. g., Xu, Y. y., Yu, H. Q ,.Xin, X. d., Wei, Q., Du, B., 2010. Adsorption of phosphate from aqueous solution by hydroxy-aluminum, hydroxy-iron and hydroxy-iron–aluminum pillared bentonites. Journal of Hazardous Materials. 179, 244-250.
  41. Yoon, S.-Y., Lee, C.-G., Park, J.-A., Kim, J.-H., Kim, S.-B., Lee, S.-H., Choi, J.-W., 2014. Kinetic ,
  42. equilibrium and thermodynamic studies for phosphate adsorption to magnetic iron oxide nanoparticles. Chemical Engineering Journal. 236, 341-347.
  43. Zhang, X., Lin, S., Chen, Z., Megharaj, M. and Naidu, R., 2011. Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: reactivity, characterization and mechanism, Water Research. 45, 3481–3488.
  44. Zhang, Y., Li, Y., Dai, C., Zhou, X., and Zhang, W. X. 2014. Sequestration of Cd (II) with Nanoscale Zero-valent Iron (nZVI): Characterization and Test in a two-stage system. Chemical Engineering Journal. 244: 218–226.