Investigations into the Adsorption Isotherm and Kinetics of Heavy Metal Removal Using Green Iron Oxide Nanoparticles.

Kirti Srivastava; Roli Verma; R.S. Jagadish; Yamini Pandey; Abhishek Kumar

doi:10.37819/nanofab.10.2050

Investigations into the Adsorption Isotherm and Kinetics of Heavy Metal Removal Using Green Iron Oxide Nanoparticles.

Kirti Srivastava

Roli Verma

R.S. Jagadish

Yamini Pandey

Abhishek Kumar

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Abstract

Iron oxide nanoparticles (IONPs) are highly effective and environmentally sustainable adsorbents for the removal of heavy metals from wastewater. This study focuses on exploring a green route for synthesizing IONPs using Hibiscus rosa-sinensis petal extract, promoting an eco-friendly approach. The synthesized particles were evaluated analytically using XRD, confirming a crystallite size of 6.16 nm, and were assessed for adsorption of Pb(II) and Cu(II) ions. Optimized adsorption conditions, including pH 5 and an interaction period of 30 minutes, resulted in high removal efficiencies of 95.48% for Pb(II) and 84.9% for Cu(II). Adsorption behavior was best explained by the Langmuir isotherm, revealing maximum adsorption capacities of 30.77 mg/g and 28.74 mg/g for Pb(II) and Cu(II) respectively, while kinetic studies confirmed a pseudo-second-order model. These findings underscore the potency of green-synthesized IONPs as a promising and sustainable solution for wastewater treatment, paving the way for their potential real-world applications.

Keywords: Green iron oxide nanoparticles Heavy metals Adsorption Chemical kinetics Isotherm

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References

1. Almeida, A. C. M., do Nascimento, R. A., Amador, I. C. B., de Sousa Santos, T. C., Martelli, M. C., de Faria, L. J. G., & da Paixão Ribeiro, N. F. (2021). Chemically activated red mud: assessing structural modifications and optimizing adsorption properties for hexavalent chromium. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 628, 127325.
2. Al-Zboon, K., Al-Harahsheh, M. S., & Hani, F. B. (2011). Fly ash-based geopolymer for Pb removal from aqueous solution. Journal of hazardous materials, 188(1-3), 414-421.
3. Arora, R. (2019). Adsorption of heavy metals–a review. Materials Today: Proceedings, 18, 4745-4750.
4. Carrott, P. J. M., & Carrott, M. R. (2007). Lignin–from natural adsorbent to activated carbon: a review. Bioresource technology, 98(12), 2301-2312.
5. Chen, S. Y., Chen, W. H., & Shih, C. J. (2008). Heavy metal removal from wastewater using zero-valent iron nanoparticles. Water Science and Technology, 58(10), 1947-1954.
6. Da Costa, G. M., De Grave, E., De Bakker, P. M. A., & Vandenberghe, R. E. (1994). Synthesis and characterization of some iron oxides by sol-gel method. Journal of Solid State Chemistry, 113(2), 405-412.
7. Deliyanni, E. A., Kyzas, G. Z., Triantafyllidis, K. S., & Matis, K. A. (2015). Activated carbons for the removal of heavy metal ions: A systematic review of recent literature focused on lead and arsenic ions. Open Chemistry, 13(1), 000010151520150087.
8. Drinking water standard and health advisories table, SanFrancisco; United States Environmental ProtectionAgency (USEPA),2007.
9. Eyvaz, M., Albahnasawi, A., Gürbulak, E., & Yüksel, E. (Eds.). (2022). Water Conservation: Inevitable Strategy. BoD–Books on Demand.
10. Fu, F., & Wang, Q. (2011). Removal of heavy metal ions from wastewaters: a review. Journal of environmental management, 92(3), 407-418.
11. Gu, S., Kang, X., Wang, L., Lichtfouse, E., & Wang, C. (2019). Clay mineral adsorbents for heavy metal removal from wastewater: a review. Environmental Chemistry Letters, 17, 629-654.
12. Gupta, K., Joshi, P., Gusain, R., & Khatri, O. P. (2021). Recent advances in adsorptive removal of heavy metal and metalloid ions by metal oxide-based nanomaterials. Coordination Chemistry Reviews, 445, 214100.
13. Gupta, V. K., & Sharma, S. (2002). Removal of cadmium and zinc from aqueous solutions using red mud. Environmental Science & Technology, 36(16), 3612-3617.
14. Ho, Y. S., & McKay, G. (2000). The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water research, 34(3), 735-742.
15. Hou, C. L., Li, T. H., Zhao, T. K., Liu, H. G., Liu, L. H., & Zhang, W. J. (2013). Electromagnetic wave absorbing properties of multi-wall carbon nanotube/Fe3O4 hybrid materials. New Carbon Materials, 28(3), 184-190. In: Drioli, E., Giorno, L. (eds) Encyclopedia of Membranes. Springer, Berlin, Heidelberg.
16. Indian standard drinking water speciﬁcations, (2nd Eds.), NewDelhi,India;BureauofIndianStandards(BIS),2012.
17. Irannajad, M., & Kamran Haghighi, H. (2021). Removal of heavy metals from polluted solutions by zeolitic adsorbents: a review. Environmental Processes, 8, 7-35.
18. Latha, N., & Gowri, M. (2014). Biosynthesis and characterisation of Fe3O4 nanoparticles using Caricaya papaya leaves extract. Int J Sci Res, 3(11), 1551-1556.
19. Lesiak, B., Rangam, N., Jiricek, P., Gordeev, I., Tóth, J., Kövér, L., ... & Borowicz, P. (2019). Surface study of Fe3O4 nanoparticles functionalized with biocompatible adsorbed molecules. Frontiers in chemistry, 7, 642.
20. Namasivayam, C., & Ranganathan, K. (1998). Effect of organic ligands on the removal of Pb (II), Ni (II) and Cd (II) by ‘waste’Fe (III)/Cr (III) hydroxide. Water Research, 32(3), 969-971.
21. Namasivayam, C., & Yamuna, R. T. (1995). Waste biogas residual slurry as an adsorbent for the removal of Pb (II) from aqueous solution and radiator manufacturing industry wastewater. Bioresource Technology, 52(2), 125-131.
22. Niraimathee, V. A., Subha, V., Ravindran, R. E., & Renganathan, S. (2016). Green synthesis of iron oxide nanoparticles from Mimosa pudica root extract. International Journal of Environment and Sustainable Development, 15(3), 227-240.
23. Nizamuddin, S., Siddiqui, M. T. H., Mubarak, N. M., Baloch, H. A., Abdullah, E. C., Mazari, S. A., ... & Tanksale, A. (2019). Iron oxide nanomaterials for the removal of heavy metals and dyes from wastewater. Nanoscale materials in water purification, 447-472.
24. Nuhoğlu, Y., Ekmekyapar Kul, Z., Kul, S., Nuhoğlu, Ç., & Ekmekyapar Torun, F. (2021). Pb (II) biosorption from the aqueous solutions by raw and modified tea factory waste (TFW). International Journal of Environmental Science and Technology, 1-12.
25. Prasad, C., Karlapudi, S., Rao, C. N., Venkateswarlu, P., & Bahadur, I. (2017). A highly resourceful magnetically separable magnetic nanoparticles from aqueous peel extract of Bottle gourds for organic dyes degradation. Journal of Molecular Liquids, 243, 611-615.
26. Sabaté Reboll, J. (2016). Heavy metal recovery by chelating agents and membranes.
27. Semerjian, L. (2018). Removal of heavy metals (Cu, Pb) from aqueous solutions using pine (Pinus halepensis) sawdust: Equilibrium, kinetic, and thermodynamic studies. Environmental technology & innovation, 12, 91-103.
28. Shi, D., Yang, H., Ji, S., Jiang, S., Liu, X., & Zhang, D. (2015). Preparation and characterization of core-shell structure Fe3O4@ C magnetic nanoparticles. Procedia engineering, 102, 1555-1562.
29. Shojaee, S., & Shahri, M. M. (2016). Green synthesis and characterization of iron oxide magnetic nanoparticles using Shanghai white tea (Camelia sinensis) aqueous extract.
30. Singh, A. K., Srivastava, O. N., & Singh, K. (2017). Shape and size-dependent magnetic properties of Fe 3 O 4 nanoparticles synthesized using piperidine. Nanoscale research letters, 12, 1-7.
31. Singh, S., Kapoor, D., Khasnabis, S., Singh, J., & Ramamurthy, P. C. (2021). Mechanism and kinetics of adsorption and removal of heavy metals from wastewater using nanomaterials. Environmental Chemistry Letters, 19(3), 2351-2381.
32. Singh, S., Kumar, V., Romero, R., Sharma, K., & Singh, J. (2019). Applications of nanoparticles in wastewater treatment. Nanobiotechnology in bioformulations, 395-418.
33. Sivashankar, R., Sathya, A. B., Vasantharaj, K., & Sivasubramanian, V. (2014). Magnetic composite an environmental super adsorbent for dye sequestration–A review. Environmental Nanotechnology, Monitoring & Management, 1, 36-49.
34. Srivastava, K., Srivastava, A., Singh, P., & Sharma, V. (2021). Remediation of distillery waste water using zero valent iron nanoparticles. Current Research in Green and Sustainable Chemistry, 4, 100072.
35. Srivastava, K., Srivastava, A., & Singh, P.. (2022). Kinetic and Adsorption Isotherm studies for the removal of Heavy Metals by Rhizoclonium Species.RJPBCS,13,4,56-63. https://doi.org/10.33887/rjpbcs/2022.13.4.1
36. Srivastava, S. K., Gupta, V. K., & Mohan, D. (1997). Removal of lead and chromium by activated slag—a blast-furnace waste. Journal of Environmental Engineering, 123(5), 461-468.
37. Subramani, B. S., Shrihari, S., Manu, B., & Babunarayan, K. S. (2019). Evaluation of pyrolyzed areca husk as a potential adsorbent for the removal of Fe2+ ions from aqueous solutions. Journal of environmental management, 246, 345-354.
38. Sugumaran, M., Poornima, M., & Sethuvani, S. (2012). Phytochemical and trace element analysis of Hibiscus rosa sinensis Linn and Hibiscus syriacus Linn flowers. NPAIJ, 8(9), 341-345.
39. Thirunavukkarasu, A., Nithya, R., & Sivashankar, R. (2020). A review on the role of nanomaterials in the removal of organic pollutants from wastewater. Reviews in Environmental Science and Bio/Technology, 19(4), 751-778.
40. Venkateswarlu, S., Kumar, B. N., Prasad, C. H., Venkateswarlu, P., & Jyothi, N. V. V. (2014). Bio-inspired green synthesis of Fe3O4 spherical magnetic nanoparticles using Syzygium cumini seed extract. Physica B: Condensed Matter, 449, 67-71.
41. Wang, S., Li, L., & Zhu, Z. H. (2007). Solid-state conversion of fly ash to effective adsorbents for Cu removal from wastewater. Journal of hazardous materials, 139(2), 254-259.
42. Wang, X., Zheng, Y., & Wang, A. (2009). Fast removal of copper ions from aqueous solution by chitosan-g-poly (acrylic acid)/attapulgite composites. Journal of Hazardous Materials, 168(2-3), 970-977.
43. Zargoosh, K., Abedini, H., Abdolmaleki, A., & Molavian, M. R. (2013). Effective removal of heavy metal ions from industrial wastes using thiosalicylhydrazide-modified magnetic nanoparticles. Industrial & Engineering Chemistry Research, 52(42), 14944-14954.
44. Zhang, Y., Wang, Y., Zhang, H., Li, Y., Zhang, Z., & Zhang, W. (2020). Recycling spent lithium-ion battery as adsorbents to remove aqueous heavy metals: Adsorption kinetics, isotherms, and regeneration assessment. Resources, Conservation and Recycling, 156, 104688.

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Investigations into the Adsorption Isotherm and Kinetics of Heavy Metal Removal Using Green Iron Oxide Nanoparticles. (2025). Nanofabrication, 10. https://doi.org/10.37819/nanofab.10.2050

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Investigations into the Adsorption Isotherm and Kinetics of Heavy Metal Removal Using Green Iron Oxide Nanoparticles. (2025). Nanofabrication, 10. https://doi.org/10.37819/nanofab.10.2050

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[1] 1. Almeida, A. C. M., do Nascimento, R. A., Amador, I. C. B., de Sousa Santos, T. C., Martelli, M. C., de Faria, L. J. G., & da Paixão Ribeiro, N. F. (2021). Chemically activated red mud: assessing structural modifications and optimizing adsorption properties for hexavalent chromium. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 628, 127325.

[2] 2. Al-Zboon, K., Al-Harahsheh, M. S., & Hani, F. B. (2011). Fly ash-based geopolymer for Pb removal from aqueous solution. Journal of hazardous materials, 188(1-3), 414-421.

[3] 3. Arora, R. (2019). Adsorption of heavy metals–a review. Materials Today: Proceedings, 18, 4745-4750.

[4] 4. Carrott, P. J. M., & Carrott, M. R. (2007). Lignin–from natural adsorbent to activated carbon: a review. Bioresource technology, 98(12), 2301-2312.

[5] 5. Chen, S. Y., Chen, W. H., & Shih, C. J. (2008). Heavy metal removal from wastewater using zero-valent iron nanoparticles. Water Science and Technology, 58(10), 1947-1954.

[6] 6. Da Costa, G. M., De Grave, E., De Bakker, P. M. A., & Vandenberghe, R. E. (1994). Synthesis and characterization of some iron oxides by sol-gel method. Journal of Solid State Chemistry, 113(2), 405-412.

[7] 7. Deliyanni, E. A., Kyzas, G. Z., Triantafyllidis, K. S., & Matis, K. A. (2015). Activated carbons for the removal of heavy metal ions: A systematic review of recent literature focused on lead and arsenic ions. Open Chemistry, 13(1), 000010151520150087.

[8] 8. Drinking water standard and health advisories table, SanFrancisco; United States Environmental ProtectionAgency (USEPA),2007.

[9] 9. Eyvaz, M., Albahnasawi, A., Gürbulak, E., & Yüksel, E. (Eds.). (2022). Water Conservation: Inevitable Strategy. BoD–Books on Demand.

[10] 10. Fu, F., & Wang, Q. (2011). Removal of heavy metal ions from wastewaters: a review. Journal of environmental management, 92(3), 407-418.

[11] 11. Gu, S., Kang, X., Wang, L., Lichtfouse, E., & Wang, C. (2019). Clay mineral adsorbents for heavy metal removal from wastewater: a review. Environmental Chemistry Letters, 17, 629-654.

[12] 12. Gupta, K., Joshi, P., Gusain, R., & Khatri, O. P. (2021). Recent advances in adsorptive removal of heavy metal and metalloid ions by metal oxide-based nanomaterials. Coordination Chemistry Reviews, 445, 214100.

[13] 13. Gupta, V. K., & Sharma, S. (2002). Removal of cadmium and zinc from aqueous solutions using red mud. Environmental Science & Technology, 36(16), 3612-3617.

[14] 14. Ho, Y. S., & McKay, G. (2000). The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water research, 34(3), 735-742.

[15] 15. Hou, C. L., Li, T. H., Zhao, T. K., Liu, H. G., Liu, L. H., & Zhang, W. J. (2013). Electromagnetic wave absorbing properties of multi-wall carbon nanotube/Fe3O4 hybrid materials. New Carbon Materials, 28(3), 184-190. In: Drioli, E., Giorno, L. (eds) Encyclopedia of Membranes. Springer, Berlin, Heidelberg.

[16] 16. Indian standard drinking water speciﬁcations, (2nd Eds.), NewDelhi,India;BureauofIndianStandards(BIS),2012.

[17] 17. Irannajad, M., & Kamran Haghighi, H. (2021). Removal of heavy metals from polluted solutions by zeolitic adsorbents: a review. Environmental Processes, 8, 7-35.

[18] 18. Latha, N., & Gowri, M. (2014). Biosynthesis and characterisation of Fe3O4 nanoparticles using Caricaya papaya leaves extract. Int J Sci Res, 3(11), 1551-1556.

[19] 19. Lesiak, B., Rangam, N., Jiricek, P., Gordeev, I., Tóth, J., Kövér, L., ... & Borowicz, P. (2019). Surface study of Fe3O4 nanoparticles functionalized with biocompatible adsorbed molecules. Frontiers in chemistry, 7, 642.

[20] 20. Namasivayam, C., & Ranganathan, K. (1998). Effect of organic ligands on the removal of Pb (II), Ni (II) and Cd (II) by ‘waste’Fe (III)/Cr (III) hydroxide. Water Research, 32(3), 969-971.

[21] 21. Namasivayam, C., & Yamuna, R. T. (1995). Waste biogas residual slurry as an adsorbent for the removal of Pb (II) from aqueous solution and radiator manufacturing industry wastewater. Bioresource Technology, 52(2), 125-131.

[22] 22. Niraimathee, V. A., Subha, V., Ravindran, R. E., & Renganathan, S. (2016). Green synthesis of iron oxide nanoparticles from Mimosa pudica root extract. International Journal of Environment and Sustainable Development, 15(3), 227-240.

[23] 23. Nizamuddin, S., Siddiqui, M. T. H., Mubarak, N. M., Baloch, H. A., Abdullah, E. C., Mazari, S. A., ... & Tanksale, A. (2019). Iron oxide nanomaterials for the removal of heavy metals and dyes from wastewater. Nanoscale materials in water purification, 447-472.

[24] 24. Nuhoğlu, Y., Ekmekyapar Kul, Z., Kul, S., Nuhoğlu, Ç., & Ekmekyapar Torun, F. (2021). Pb (II) biosorption from the aqueous solutions by raw and modified tea factory waste (TFW). International Journal of Environmental Science and Technology, 1-12.

[25] 25. Prasad, C., Karlapudi, S., Rao, C. N., Venkateswarlu, P., & Bahadur, I. (2017). A highly resourceful magnetically separable magnetic nanoparticles from aqueous peel extract of Bottle gourds for organic dyes degradation. Journal of Molecular Liquids, 243, 611-615.

[26] 26. Sabaté Reboll, J. (2016). Heavy metal recovery by chelating agents and membranes.

[27] 27. Semerjian, L. (2018). Removal of heavy metals (Cu, Pb) from aqueous solutions using pine (Pinus halepensis) sawdust: Equilibrium, kinetic, and thermodynamic studies. Environmental technology & innovation, 12, 91-103.

[28] 28. Shi, D., Yang, H., Ji, S., Jiang, S., Liu, X., & Zhang, D. (2015). Preparation and characterization of core-shell structure Fe3O4@ C magnetic nanoparticles. Procedia engineering, 102, 1555-1562.

[29] 29. Shojaee, S., & Shahri, M. M. (2016). Green synthesis and characterization of iron oxide magnetic nanoparticles using Shanghai white tea (Camelia sinensis) aqueous extract.

[30] 30. Singh, A. K., Srivastava, O. N., & Singh, K. (2017). Shape and size-dependent magnetic properties of Fe 3 O 4 nanoparticles synthesized using piperidine. Nanoscale research letters, 12, 1-7.

[31] 31. Singh, S., Kapoor, D., Khasnabis, S., Singh, J., & Ramamurthy, P. C. (2021). Mechanism and kinetics of adsorption and removal of heavy metals from wastewater using nanomaterials. Environmental Chemistry Letters, 19(3), 2351-2381.

[32] 32. Singh, S., Kumar, V., Romero, R., Sharma, K., & Singh, J. (2019). Applications of nanoparticles in wastewater treatment. Nanobiotechnology in bioformulations, 395-418.

[33] 33. Sivashankar, R., Sathya, A. B., Vasantharaj, K., & Sivasubramanian, V. (2014). Magnetic composite an environmental super adsorbent for dye sequestration–A review. Environmental Nanotechnology, Monitoring & Management, 1, 36-49.

[34] 34. Srivastava, K., Srivastava, A., Singh, P., & Sharma, V. (2021). Remediation of distillery waste water using zero valent iron nanoparticles. Current Research in Green and Sustainable Chemistry, 4, 100072.

[35] 35. Srivastava, K., Srivastava, A., & Singh, P.. (2022). Kinetic and Adsorption Isotherm studies for the removal of Heavy Metals by Rhizoclonium Species.RJPBCS,13,4,56-63. https://doi.org/10.33887/rjpbcs/2022.13.4.1

[36] 36. Srivastava, S. K., Gupta, V. K., & Mohan, D. (1997). Removal of lead and chromium by activated slag—a blast-furnace waste. Journal of Environmental Engineering, 123(5), 461-468.

[37] 37. Subramani, B. S., Shrihari, S., Manu, B., & Babunarayan, K. S. (2019). Evaluation of pyrolyzed areca husk as a potential adsorbent for the removal of Fe2+ ions from aqueous solutions. Journal of environmental management, 246, 345-354.

[38] 38. Sugumaran, M., Poornima, M., & Sethuvani, S. (2012). Phytochemical and trace element analysis of Hibiscus rosa sinensis Linn and Hibiscus syriacus Linn flowers. NPAIJ, 8(9), 341-345.

[39] 39. Thirunavukkarasu, A., Nithya, R., & Sivashankar, R. (2020). A review on the role of nanomaterials in the removal of organic pollutants from wastewater. Reviews in Environmental Science and Bio/Technology, 19(4), 751-778.

[40] 40. Venkateswarlu, S., Kumar, B. N., Prasad, C. H., Venkateswarlu, P., & Jyothi, N. V. V. (2014). Bio-inspired green synthesis of Fe3O4 spherical magnetic nanoparticles using Syzygium cumini seed extract. Physica B: Condensed Matter, 449, 67-71.

[41] 41. Wang, S., Li, L., & Zhu, Z. H. (2007). Solid-state conversion of fly ash to effective adsorbents for Cu removal from wastewater. Journal of hazardous materials, 139(2), 254-259.

[42] 42. Wang, X., Zheng, Y., & Wang, A. (2009). Fast removal of copper ions from aqueous solution by chitosan-g-poly (acrylic acid)/attapulgite composites. Journal of Hazardous Materials, 168(2-3), 970-977.

[43] 43. Zargoosh, K., Abedini, H., Abdolmaleki, A., & Molavian, M. R. (2013). Effective removal of heavy metal ions from industrial wastes using thiosalicylhydrazide-modified magnetic nanoparticles. Industrial & Engineering Chemistry Research, 52(42), 14944-14954.

[44] 44. Zhang, Y., Wang, Y., Zhang, H., Li, Y., Zhang, Z., & Zhang, W. (2020). Recycling spent lithium-ion battery as adsorbents to remove aqueous heavy metals: Adsorption kinetics, isotherms, and regeneration assessment. Resources, Conservation and Recycling, 156, 104688.