Experimental Study of 4-Nonylphenol Removal from Aquatic Solutions Using Graphene Oxide Chitosan Aerogel Beads

Document Type : Research Paper


1 PhD Student, Dept. of Environmental Science (Pollution), Faculty of Natural Resources and Environment, Science and Research Branch, Islamic Azad University, Tehran, Iran

2 Assoc. Prof., School of Environment, College of Engineering, University of Tehran, Tehran, Iran

3 Assoc. Prof., Dept. of Environmental Science, Faculty of Natural Resources and Environment, Science and Research Branch, Islamic Azad University, Tehran, Iran

4 Prof., Dept. of Chemistry, College of Basic Sciences, Central Tehran Branch, Islamic Azad University, Tehran, Iran


4-Nonylphenol (4-NP) as one of the most abundant and toxic alkylphenols is the most effective of endocrine disruptive compounds. It is produced in high quantities and then enters the aquatic environment via discharge of sewage treatment effluents. Therefore, its removal from surface water and municipal wastewater effluents is more commonly considered. This study has been done with the aim of the investigation of the grapheneoxide chitosan aerogel beads’ performance for removal of 4-NP from aquatic solutions. In this regard, the characteristics of the synthesized nano-adsorbent have been investigated by SEM, TEM, FTIR, BET and pHpzc techniques. Then, batch adsorption experiments have been done to determine the adsorption behavior. In this method, the effect of some parameters such as adsorbent dosage, 4-NP concentration, pH, contact time, and temperature was evaluated with the aim of determining optimum conditions. The results show that the adsorption efficiency could reach 100% in 10 min at neutral pH with 1.5 mg/L of 4-NP concentration and 0.8 g/L of the adsorbent. The achieved results were compared with different kinetic and isotherm models, which found that the 4-NP adsorption by the synthesized nano-adsorbent are explained by the Pseudo-Second-Order kinetic (R2=0.9992) and Dubinin-Radushkevich isotherm (R2=0.9988) models with the adsorbents’ maximum capacity of 70.97 mg/g. Thermodynamic investigations indicated that the adsorption process was spontaneous and feasible (-ΔG), endothermic (+ΔH), and reversible (+ΔS).


Al-Ahmari, S. D., Watson, K., Fong, B. N., Ruyonga, R. M. & Ali, H. 2018. Adsorption kinetics of 4-n-nonylphenol on hematite and goethite. Journal of Environmental Chemical Engineering, 6, 4030-4036.
Asimakopoulos, A. G., Thomaidis, N. S. & Koupparis, M. A. 2012. Recent trends in biomonitoring of bisphenol A, 4-t-octylphenol, and 4-nonylphenol. Toxicology Letters, 210, 141-154.
Baghdadi, M., Ghaffari, E. & Aminzadeh, B. 2016. Removal of carbamazepine from municipal wastewater effluent using optimally synthesized magnetic activated carbon: adsorption and sedimentation kinetic studies. Journal of Environmental Chemical Engineering, 4, 3309-3321.
Bechi, N., Ietta, F., Romagnoli, R., Jantra, S., Cencini, M., Galassi, G., et al. 2010. Environmental levels of para-nonylphenol are able to affect cytokine secretion in human placenta. Environmental Health Perspectives, 118, 427-431.
Bessa, A., Gonçalves, G., Henriques, B., Domingues, E. M., Pereira, E. & Marques, P. A. 2020. Green graphene–chitosan sorbent materials for mercury water remediation. Nanomaterials, 10(8), 1474.
Cao, Y., Li, G. & Li, X. 2016. Graphene/layered double hydroxide nanocomposite: properties, synthesis and applications. Chemical Engineering Journal, 292, 207-223.
Chen, G. W., Ding, W. H., Ku, H. Y., Chao, H. R., Chen, H. Y., Huang, M. C., et al. 2010. Alkylphenols in human milk and their relations to dietary habits in central Taiwan. Food and Chemical Toxicology, 48, 1939-1944.
Cheng, Q., Zhou, Q., Jin, Z., Jiang, Y., Xu, L., Jiang, H., et al. 2019. Bioaccumulation, growth performance, and transcriptomic response of dictyosphaerium sp. after exposure to nonylphenol. Science of The Total Environment, 687, 416-422.
Chowdhury, S. & Balasubramanian, R. 2014. Recent advances in the use of graphene-family nanoadsorbents for removal of toxic pollutants from wastewater. Advances in Colloid and Interface Science, 204, 35-56.
Dada, A., Olalekan, A., Olatunya, A. & Dada, O. 2012. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk. IOSR Journal of Applied Chemistry, 3, 38-45.
Doğan, M., Alkan, M., Demirbaş, Ö., Özdemir, Y. & Özmetin, C. 2006. Adsorption kinetics of maxilon blue GRL onto sepiolite from aqueous solutions. Chemical Engineering Journal, 124, 89-101.
Dong, C. D., Chen, C. W., Tsai, M. L., Chang, J. H., Lyu, S. Y. & Hung, C. M. 2019. Degradation of 4-nonylphenol in marine sediments by persulfate over magnetically modified biochars. Bioresource Technology, 281, 143-148.
Duan, X., Wang, X., Xie, J., Feng, L., Yan, Y., Wang, F., et al. 2018. Acidogenic bacteria assisted biodegradation of nonylphenol in waste activated sludge during anaerobic fermentation for short-chain fatty acids production. Bioresource Technology, 268, 692-699.
Elshafei, G. M. S., Yehia, F. Z., Eshaq, G. & Elmetwally, A. E. 2017. Enhanced degradation of nonylphenol at neutral pH by ultrasonic assisted- heterogeneous Fenton using nano zero valent metals. Separation and Purification Technology, 178, 122-129.
USEPA. 2010. Nonylphenol (NP) and Nonylphenol Ethoxylates (NPEs) Action Plan. RIN.
Fan, Z., Shi, H., Zhao, H., Cai, J. & Zhao, G. 2018. Application of carbon aerogel electrosorption for enhanced Bi2WO6 photoelectrocatalysis and elimination of trace nonylphenol. Carbon, 126, 279-288.
Guo, D., Cai, P., Sun, J., He, W., Wu, X., Zhang, T., et al. 2016. Reduced-graphene-oxide/metal-oxide p-n heterojunction aerogels as efficient 3D sensing frameworks for phenol detection. Carbon, 99, 571-578.
Han, Q., Liang, Q., Zhang, X., Yang, L. & Ding, M. 2016. Graphene aerogel based monolith for effective solid-phase extraction of trace environmental pollutants from water samples. Journal of Chromatography A, 1447, 39-46.
Hao, P., Zhao, Z., Leng, Y., Tian, J., Sang, Y., Boughton, R. I., et al. 2015. Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high performance supercapacitors. Nano Energy, 15, 9-23.
Huang, B., Liu, Y., Li, B., Liu, S., Zeng, G., Zeng, Z., et al. 2017a. Effect of Cu(II) ions on the enhancement of tetracycline adsorption by Fe3O4@SiO2-chitosan/graphene oxide nanocomposite. Carbohydrate Polymers, 157, 576-585.
Huang, Z., Li, Z., Zheng, L., Zhou, L., Chai, Z., Wang, X., et al. 2017b. Interaction mechanism of uranium(VI) with three-dimensional graphene oxide-chitosan composite: insights from batch experiments, IR, XPS, and EXAFS spectroscopy. Chemical Engineering Journal, 328, 1066-1074.
Ibekwe, C., Oyatogun, G., Esan, T. & Oluwasegun, K. 2017. Synthesis and characterization of chitosan/gum arabic nanoparticles for bone regeneration. American Journal of Materials Science and Engineering, 5, 28-36.
Jin, Z., Wang, X., Sun, Y., Ai, Y. & Wang, X. 2015. Adsorption of 4-n-nonylphenol and bisphenol-a on magnetic reduced graphene oxides: a combined experimental and theoretical studies. Environmental Science and Technology, 49, 9168-9175.
Khatibikamal, V., Panahi, H. A., Torabian, A. & Baghdadi, M. 2019a. Optimized poly(amidoamine) coated magnetic nanoparticles as adsorbent for the removal of nonylphenol from water. Microchemical Journal, 145, 508-516.
Khatibikamal, V., Torabian, A., Ahmad Panahi, H. & Baghdadi, M. 2019b. Stabilizing of poly(amidoamine) dendrimer on the surface of sand for the removal of nonylphenol from water: batch and column studies. Journal of Hazardous Materials, 367, 357-364.
Kim, Y. S. & Kim, J. H. 2019. Isotherm, kinetic and thermodynamic studies on the adsorption of paclitaxel onto Sylopute. The Journal of Chemical Thermodynamics, 130, 104-113.
Lai, K. C., Hiew, B. Y. Z., Lee, L. Y., Gan, S., Thangalazhy-Gopakumar, S., Chiu, W. S., et al. 2019. Ice-templated graphene oxide/chitosan aerogel as an effective adsorbent for sequestration of metanil yellow dye. Bioresource Technology, 274, 134-144.
Li, C., Jin, F. & Snyder, S. A. 2018a. Recent advancements and future trends in analysis of nonylphenol ethoxylates and their degradation product nonylphenol in food and environment. TrAC Trends in Analytical Chemistry, 107, 78-90.
Li, Z., Song, X., Cui, S., Jiao, Y. & Zhou, C. 2018b. Fabrication of macroporous reduced graphene oxide composite aerogels reinforced with chitosan for high bilirubin adsorption. RSC Advances, 8, 8338-8348.
Lin, Y. W., Yang, C. C., Tuan, N. N. & Huang, S. L. 2016. Diversity of octylphenol polyethoxylate-degrading bacteria: with a special reference to Brevibacterium sp. TX4. International Biodeterioration and Biodegradation, 115, 55-63.
Lou, L., Huang, Q., Lou, Y., Lu, J., Hu, B. & Lin, Q. 2019. Adsorption and degradation in the removal of nonylphenol from water by cells immobilized on biochar. Chemosphere, 228, 676-684.
Maleki, H. 2016. Recent advances in aerogels for environmental remediation applications: a review. Chemical Engineering Journal, 300, 98-118.
Marcano, D. C., Kosynkin, D. V., Berlin, J. M., Sinitskii, A., Sun, Z., Slesarev, A., et al. 2010. Improved synthesis of graphene oxide. ACS Nano, 4, 4806-4814.
Nawaz, M., Miran, W., Jang, J. & Lee, D. S. 2017. One-step hydrothermal synthesis of porous 3D reduced graphene oxide/TiO2 aerogel for carbamazepine photodegradation in aqueous solution. Applied Catalysis B: Environmental, 203, 85-95.
Ömeroğlu, S. & Sanin, F. D. 2014. Fate and degradation kinetics of nonylphenol compounds in aerobic batch digesters. Water Research, 64, 1-12.
Pan, J., Li, L., Hang, H., Ou, H., Zhang, L., Yan, Y., et al. 2013. Study on the nonylphenol removal from aqueous solution using magnetic molecularly imprinted polymers based on fly-ash-cenospheres. Chemical Engineering Journal, 223, 824-832.
Razzouki, B., El Hajjaji, S., Azzaoui, K., Errich, A., Lamhamdi, A., Berrabah, M., et al. 2015. Physicochemical study of arsenic removal using iron hydroxide. Journal of Materials and Environmental Science, 6(5), 144-150.
Tang, C., Huang, X., Wang, H., Shi, H. & Zhao, G. 2020. Mechanism investigation on the enhanced photocatalytic oxidation of nonylphenol on hydrophobic TiO2 nanotubes. Journal of Hazardous Materials, 382, 121017.
Wang, Y., Xia, G., Wu, C., Sun, J., Song, R. & Huang, W. 2015. Porous chitosan doped with graphene oxide as highly effective adsorbent for methyl orange and amido black 10B. Carbohydrate Polymers, 115, 686-693.
Xin, Y., Gao, M., Wang, Y. & Ma, D. 2014. Photoelectrocatalytic degradation of 4-nonylphenol in water with WO3/TiO2 nanotube array photoelectrodes. Chemical Engineering Journal, 242, 162-169.
Yang, S., Zhang, L., Yang, Q., Zhang, Z., Chen, B., Lv, P., et al. 2015. Graphene aerogel prepared by thermal evaporation of graphene oxide suspension containing sodium bicarbonate. Journal of Materials Chemistry A, 3, 7950-7958.
You, X., He, M., Cao, X., Wang, P., Wang, J. & Li, L. 2019. Molecular dynamics simulations of removal of nonylphenol pollutants by graphene oxide: experimental study and modelling. Applied Surface Science, 475, 621-626.
Yu, B., Xu, J., Liu, J. H., Yang, S. T., Luo, J., Zhou, Q., et al. 2013. Adsorption behavior of copper ions on graphene oxide–chitosan aerogel. Journal of Environmental Chemical Engineering, 1, 1044-1050.
Yu, R., Shi, Y., Yang, D., Liu, Y., Qu, J. & Yu, Z. Z. 2017. Graphene oxide/chitosan aerogel microspheres with honeycomb-cobweb and radially oriented microchannel structures for broad-spectrum and rapid adsorption of water contaminants. ACS Applied Materials and Interfaces, 9, 21809-21819.
Yu, Z., Peldszus, S. & Huck, P. M. 2008. Adsorption characteristics of selected pharmaceuticals and an endocrine disrupting compound-naproxen, carbamazepine and nonylphenol-on activated carbon. Water Research, 42, 2873-2882.
Zamani, S. & Tabrizi, N. S. 2015. Removal of methylene blue from water by graphene oxide aerogel: thermodynamic, kinetic, and equilibrium modeling. Research on Chemical Intermediates, 41, 7945-7963.
Zhang, L., Luo, H., Liu, P., Fang, W. & Geng, J. 2016. A novel modified graphene oxide/chitosan composite used as an adsorbent for Cr(VI) in aqueous solutions. International Journal of Biological Macromolecules, 87, 586-596.
Zhao, L., Dong, P., Xie, J., Li, J., Wu, L., Yang, S. T., et al. 2013. Porous graphene oxide–chitosan aerogel for tetracycline removal. Materials Research Express, 1, 015601.
Zhao, Y., Song, J., Wu, D., Tang, T. & Sun, Y. 2015. One-step synthesis of hydrophobic mesoporous silica and its application in nonylphenol adsorption. Journal of Physics and Chemistry of Solids, 86, 1-4.
Zhou, Q., Lei, M., Li, J., Zhao, K. & Liu, Y. 2017. Sensitive determination of bisphenol A, 4-nonylphenol and 4-octylphenol by magnetic solid phase extraction with Fe@MgAl-LDH magnetic nanoparticles from environmental water samples. Separation and Purification Technology, 182, 78-86.