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Document Type : Review Article

Authors

1 Faculty of Chemistry, Department of Chemical and Process Engineering, Wroclaw University of Science and Technology, Wroclaw, Poland

2 Department of Chemistry, Adekunle Ajasin University, Akungba-Akoko, Nigeria

3 Faculty of Environmental Engineering, Department of Environmental Protection Engineering, Warsaw University Technology, Warsaw, Poland

4 Faculty of Chemistry, Department of Biotechnology, Wroclaw University of Science and Technology, Wroclaw, Poland

5 Department of Chemistry, Federal University of Technology, Akure, Nigeria

6 Faculty of Chemistry, Department of Chemistry, Wroclaw University of Science and Technology, Wroclaw, Poland

7 Department of Microbiology, University of Abuja, Abuja, Nigeria

8 Department of Chemistry, University of Ilorin, Ilorin, Nigeria

Abstract

Clay minerals are eco-friendly adsorbent materials that are abundant in nature. The usage of nano-clay for the cleanup of contaminated water has grown recently due to its distinctive physicochemical properties and characteristics. Emerging contaminants, such as pharmaceutical residue, are not typically monitored in the environment and are not controlled in our wastewater. However, due to environmental dangers and their influence on human and aquatic life, removing pharmaceutical residues and their metabolites from wastewater has piqued attention. Several researchers have investigated the application of natural clay, clay-carbon, and clay-polymer composites, among others, to remove this specific pollutant. In addition, to enhance the adsorption efficiency of natural clay minerals, the adsorption sites can be improved by acid activation, thermal treatment, or incorporation of functional groups into the clay mineral layers, which have a strong affinity for the adsorption of pharmaceutical resides. The literature review findings show that modified clays are better adsorbents for the remediation of pharmaceutical residues in wastewater than natural clays and represent an economically viable and efficient option for the cleanup of wastewater containing this contaminant. Consequently, this review gives an inclusive overview of current trends in employing clay minerals for the remediation of pharmaceutical residues in wastewater and outlines the research gaps for future research.

Graphical Abstract

‎A Review on Natural Clay Application for Removal of Pharmaceutical Residue in Wastewater

Keywords

Main Subjects

[1] N.A. Al-Odaini, M.P. Zakaria, M.I. Yaziz, S. Surif, M. Abdulghani. The occurrence of human pharmaceuticals in wastewater effluents and surface water of Langat River and its tributaries, Malaysia. Int J Environ Anal Chem., 93 (2013) 245–264.
[2] S Wu, L Zhang, J Chen. Paracetamol in the environment and its degradation by microorganisms. Appl Microbiol Biotechnol., 96(4) (2012) 875-84.
[3] O.M. Rodriguez-Narvaez, J.M. Peralta-Hernandez, A Goonetilleke, E.R. Bandala, Treatment technologies for emerging contaminants in water: a review. Chem Eng J 323 (2017) 361–380.
[4] G.J. Zhou, L. Lin, X.Y. Li, K.M.Y. Leung .Removal of emerging contaminants from wastewater during chemically enhanced primary sedimentation and acidogenic sludge fermentation. Water Res, 175 (2020) e115646.
[5] L. Li, D. Zou, Z. Xiao, X. Zeng, L. Zhang, L. Jiang, A. Wang, D. Ge, G. Zhang, F. Liu, Biochar as a sorbent for emerging contaminants enables improvements in waste management and sustainable resource use. J Clean Prod., 210(2019) 1324–1342.
[6] J. Choina, H. Kosslick, C. Fischer, G-U Flechsig, L. Frunza, A. Schulz, Photocatalytic decomposition of pharmaceutical ibuprofen pollutions in water over titania catalyst. Appl Catal B Environ., 129 (2013) 589–598.
[7] S. Mozia, A.W. Morawski. The performance of a hybrid photocatalysis–MD system for the treatment of tap water contaminated with ibuprofen. Catal Today., 193 (2012) 213–220.
[8] D. Nasuhoglu, V. Yargeau, D. Berk, Photo-removal of sulfamethoxazole (SMX) by photolytic and photocatalytic processes in a batch reactor under UV-C radiation (k max = 254 nm). J. Hazard Mater., 186 (2011) 67–75.
[9] A. Sangion, P. Gramatica, Hazard of pharmaceuticals for the aquatic environment: prioritization by structural approaches and prediction of ecotoxicity. Environ Int., 95(2016) 131–143.
[10] G.R. Quadra, H.O. de Souza, R. dos Santos Costa, M.A. dos Santos Fernandez, pharmaceuticals reach and affect the aquatic ecosystems in Brazil? A critical review of current studies in a developing country. Environ Sci Pollut Res., 24 (2016) 1200–1218.
[11] B.D. Blair, Potential upstream strategies for the mitigation of pharmaceuticals in the aquatic environment: a brief review. Curr Environ Health Rep., 3(2016) 153–160
[12] J.L. Wilkinson, P.S. Hooda, J. Barker, S. Barton, J. Swinden, Ecotoxic pharmaceuticals, personal care products, and other emerging contaminants: a review of environmental, receptor-mediated, developmental, and epigenetic toxicity with the discussion of proposed toxicity to humans. Crit Rev Environ Sci Technol 46(2016) 336–381.
[13] S. Castiglioni, R. Bagnati, R. Fanelli, F. Pomati, D. Calamari, E. Zuccato, Removal of pharmaceuticals in sewage treatment plants in Italy, Environ. Sci. Technol., 40 (2006) 357–363.
[14] F. Lu, D. Astruc, Nanocatalysts and other nanomaterials for water remediation from organic pollutants. Coordination Chemistry Reviews, 408 (2020) e213180.
[15] J.O. Straub .Reduction in the environmental exposure of pharmaceuticals through diagnostics, Personalised Healthcare, and other approaches. A mini-review and discussion paper. Sustain Chem Pharm., 3 (2016) 1–7.
[16] H. Bagheri, A. Afkhami, A. Noroozi, Removal of pharmaceutical compounds from hospital wastewaters using nanomaterials: a review. Anal Bioanal Chem Res., 3 (2016)1–18.
[17] K. Helwig, C. Hunter, M. McNaughtan, J. Roberts, O. Pahl, Ranking prescribed pharmaceuticals in terms of environmental risk: inclusion of hospital data and the importance of regular review. Environ Toxicol Chem., 35 (2016) 1043–1050.
[18] E. Moctezuma, E. Leyva, C.A. Aguilar, R.A. Luna, C. Montalvo, Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism. J Hazard Mater., 243 (2012) 130–138.
[19] M. Bundschuh, T. Hahn, B. Ehrlich, S. Ho¨ltge, R. Kreuzig, R. Schulz, Acute toxicity and environmental risks of five veterinary pharmaceuticals for aquatic macroinvertebrates. Bull Environ Contam Toxicol., 96 (2016) 139–143.
[20] W.J. Sim, J.W. Lee, E.S. Lee, S.K. Shin, S.R. Hwang, J.E. Oh. Occurrence and distribution of pharmaceuticals in wastewater from households, livestock farms, hospitals, and pharmaceutical manufacturers. Chemosphere., 82(2011)179–186.
[21] K. Kummerer, Drugs in the environment: emission of drugs, diagnostic aids, and disinfectants into wastewater by hospitals in relation to other sourcesa review. Chemosphere 45 (2001) 957–969.
[22] M. Abella´n, J. Gime´nez, S. Esplugas, Photocatalytic degradation of antibiotics: the case of sulfamethoxazole and trimethoprim. Catal Today., 144 (2009) 131–136.
[23] S. Fukahori, T. Fujiwara, R. Ito, N. Funamizu, Photocatalytic decomposition of crotamiton over aqueous TiO2 suspensions: determination of intermediates and the reaction pathway. Chemosphere., 89 (2012) 213–220.
[24] T. Yang, L. Sheng, Y. Wang, K.N. Wyckoff, C. He, Q. He, Characteristics of cadmium sorption by heat-activated red mud in aqueous solution. Sci. Rep., 8 (2018) e13558.
[25] H.E. LA Ioannou, M.I. Vasquez, D. Mantzavinos, D. Fatta-Kassinos, Solar/TiO2 photocatalytic decomposition of beta-blockers atenolol and propranolol in water and wastewater. Sol Energy., 85 (2011) 1915–1926.
[26] K. K’oreje, L. Vergeynst, D. Ombaka, P. De Wispelaere, M. Okoth, H. Van Langenhove, K. Demeestere, Occurrence patterns of pharmaceutical residues in wastewater, surface water and groundwater of Nairobi and Kisumu city, Kenya. Chemosphere., 149 (2016) 238–244.
[27] A. Khataee, M. Fathinia , S. Joo. Simultaneous monitoring of photocatalysis of three pharmaceuticals by immobilized TiO2 nanoparticles: chemometric assessment, intermediates identification, and ecotoxicological evaluation. Spectrochim Acta Part A Mol Biomol Spectrosc., 112 (2013) 33–45.
[28] D. Chen, Y. Cheng, N. Zhou, P. Chen, Y.Wang, K. Li, S. Huo, P. Cheng, P. Peng, R. Zhang, L. Wang, H. Liu, Y. Liu, R. Ruan, Photocatalytic degradation of organic pollutants using TiO2-based photocatalysts: A review, Journal of Cleaner Production, 268 (2020) e121725.
[29] Y. Zhang, W. Guo, Z. Yue, L. Lin, F. Zhao, P. Chen, W. Wu, H. Zhu, B. Yang, Y. Kuang, J. Wang. Rapid determination of 54 pharmaceutical and personal care products in fish samples using microwave-assisted extraction-Hollow fiber Liquid/solid phase microextraction, Journal of Chromatography B, 1051 (2017) 41–53.
[30] F.M.M. Salama, K.A.M. Attia, R.A.M. Said, A.M. El-Attar. First derivative synchronous fluorescence spectroscopy for the determination of Gatifloxacin in presence of its oxidative degradation product: Application to a pharmaceutical preparation. SpectrochimicaActa Part A: Molecular and Biomolecular Spectroscopy, 206 (2019) 302–313.
[31]  J. Wu, B. Wang, G. Cagnetta, J. Huang, Y. Wang, S. Deng, G. Yu. Nanoscale zero-valent iron activated persulfate coupled with Fenton oxidation process for typical pharmaceuticals and personal care products degradation. Separation and Purification Technology, (2020) e116534.
[32] A. Barra Caracciolo, E. Topp, P. Grenni. Pharmaceuticals in the environment: Biodegradation and effects on natural microbial communities, A review, Journal of Pharmaceutical and Biomedical Analysis, 106 (2015) 25–36.
[33] T.P. Wood, A.E. Basson, C. Duvenage, E.R. Rohwer. The chlorination behavior and environmental fate of the antiretroviral drug nevirapine in South African surface water. Water Research, 104 (2016) 349–360.
[34] W.L. Chen, J.Y. Cheng, X.Q. Lin. Systematic screening and identification of the chlorinated transformation products of aromatic pharmaceuticals and personal care products using high-resolution mass spectrometry. Science of the Total Environment, 637-638 (2018) 253–263.
[35] M.J. McKie, S.A. Andrews, R.C. Andrews. Conventional drinking water treatment and direct biofiltration for the removal of pharmaceuticals and artificial sweeteners: A pilot-scale approach. Science of The Total Environment, 544 (2016) 10–17.
[36] J. Fu, W.N. Lee, C. Coleman, K. Nowack, J. Carter, C.H. Huang. Removal of pharmaceuticals and personal care products by two-stage biofiltration for drinking water treatment. Science of the Total Environment, 664 (2019) 240–248.
[37] Y.L. Lin, J.H. Chiou, C.H. Lee. Effect of silica fouling on the removal of pharmaceuticals and personal care products by nanofiltration and reverse osmosis membranes. Journal of Hazardous Materials, 277 (2014) 102–109.
[38] Y.L. Lin. Effects of organic, biological, and colloidal fouling on the removal of pharmaceuticals and personal care products by nanofiltration and reverse osmosis membranes. Journal of Membrane Science, 542 (2017)342–351.
[39] L.R. Licona, J.V. Geaquinto, N.G. Nicolini, S.C. Figueiredo, A.C. Chiapetta, V. Yokoyama. Assessing the potential of nanofiltration and reverse osmosis for the removal of toxic pharmaceuticals from water. Journal of Water Process Engineering, 25 (2018) 195–204.
[40]  G. Loos, T. Scheers, K. Van Eyck, A. Van Schepdael , E. Adams, B. Van der Bruggen, R. Dewil. Electrochemical oxidation of key pharmaceuticals using a boron-doped diamond electrode. Separation and Purification Technology, 195 (2018) 184–191.
[41] M.A. López Zavala, D.A. Vega, J.M. Álvarez Vega, O.F. Castillo Jerez, R.A. Cantú Hernández. Electrochemical oxidation of acetaminophen and its transformation products in surface water: effect of pH and current density. Heliyon, 6(2) (2020) e03394.
[42] M. Ferchichi, H. Dhaouadi. Sorption of paracetamol onto biomaterials, Water Science and Technology, 74 (1) (2016) 287–294.
[43] T.M. Darweesh, and M.J. Ahmed. Batch and fixed bed adsorption of levofloxacin on granular activated carbon from date (Phoenix dactylifera L.) stones by KOH chemical activation. Environmental Toxicology and Pharmacology, 50 (2017) 159–166.
[44] A. Maged, J. Iqbal, S. Kharbish, I.S. Ismael, A. Bhatnagar. Tuning tetracycline removal from aqueous solution onto activated 2:1 layered clay mineral: Characterization, sorption, and mechanistic studies. J Hazard Mater 384: (2020) e121320.
[45] E. Abu-Danso, S. Peräniemi, T. Leiviskä, T.Y. Kim, K.M. Tripathi, A. Bhatnagar.  Synthesis of clay-cellulose biocomposite for the removal of toxic metal ions from aqueous medium. J Hazard Mater 381(2020) e120871.
[46] S.I. Felycia, E. Soetaredjo, A. Ayucitra. Clay materials for environmental remediation. Springer International Publishing, Berlin Freundlich H (1924) Kolloidchemie und Biologie. Naturwissenschaften 12 (2015) 233–239.
[47]  Z. Li, H Hong, L. Liao, C.J. Ackley, L.A. Schulz, R.A. MacDonald, A.L. Mihelich, S.M. Emard. A mechanistic study of ciprofloxacin removal by kaolinite. Colloids Surf B: Biointerfaces 88(2011) 339–344.
[48] S. Rakshit, D. Sarkar, E.J. Elzinga, P. Punamiya, R. Datta. Mechanisms of ciprofloxacin removal by nano-sized magnetite. J Hazard Mater 246–247 (2013) 221–226.
[49] D. Yin, Z. Xu, J. Shi, L. Shen, Z. He. Adsorption characteristics of ciprofloxacin on the schorl: kinetics, thermodynamics, the effect of metal ion and mechanisms. J Water Reuse Desalin 8(2018)350–359.
[50] W. Duan, N. Wang, W. Xiao, Y. Zhao, Y. Zheng. Ciprofloxacin adsorption onto different micro-structured tourmaline, halloysite, and biotite. J Mol Liq., 269 (2018) 874–881.
[51] M. Wu, S. Zhao, R. Jing, Y. Shao, X. Liu, F. Lv, X. Hu, Q. Zhang, Z. Meng, A. Liu. Competitive adsorption of antibiotic tetracycline and ciprofloxacin on montmorillonite. Appl Clay Sci 180(2019)105175.
[52] J. Liu, N. Wang, H. Zhang, and J. Baeyens. Adsorption of Congo red dye on FexCo3-xO4 nanoparticles. Journal of Environmental Management, 238(2019) 473–483.
[53] R. Xu, M. Su, Y. Liu, Z. Chen, M.Yang, D. Chen. Comparative study on the removal of different-type organic pollutants on hierarchical tetragonal bismutite microspheres: Adsorption, degradation, and mechanism. Journal of Cleaner Production, 242(2020) e118366.
[54] F. Yu, Y. Li, S. Han, J.Ma, Adsorptive removal of antibiotics from aqueous solution using carbon materials, Chemosphere 153 (2016) 365–385.
[55] K. Majeed, M. Jawaid, A. Hassan, A.A. Bakar, H.A. Khalil, A.A. Salema, I. Inuwa, Potential materials for food packaging from nanoclay/natural fibers filled hybrid composites. Mater Des 46(2013)391–410.
[57] Q.H. Zeng, A.B. Yu, G.Q. Lu, D.R. Paul, Clay-based polymer nanocomposites: research and commercial development. J Nanosci Nanotechnol 5(2005) (10):00.
[58] M.S. Nazir, M.H. Kassim, L. Mohapatra, M.A. Gilani, M.R. Raza,  & K. Majeed,  Characteristic Properties of Nanoclays and Characterization of Nanoparticulates and Nanocomposites. Composites (2016) 35–55.
[59] A. Awasthi, P. Jadhao, & K. Kumari, Clay nano-adsorbent: structures, applications, and mechanism for water treatment. SN Applied. Science. 1(2019) 1076
[60] K.K. Kennedy, K.J. Maseka, & M. Mbulo, Selected Adsorbents for Removal of Contaminants from Wastewater: Towards Engineering Clay Minerals. Open Journal of Applied Sciences, 8 (2018) 355-369.
[61] C.L. Zhang, G.L. Qiao, F. Zhao, Y. Wang, Thermodynamic and kinetic parameters of ciprofloxacin adsorption onto modified coal fly ash from aqueous solution. Journal of Molecular Liquids, 163 (2010) 53–56.
[62] G.R. Mitchell, A. Tojeria, Controlling the morphology of polymers: multiple scales of structure and processing. Springer, Berlin (2016).
[63] F. Bergaya, G. Lagaly, General introduction: Clays, clay minerals and clay science. Handbook of clay science., 1 (2006)1-8
[64] S. Ismadji, F.E. Soetaredjo, A. Ayucitra, The characterization of clay minerals and adsorption mechanism onto clays. Clay Materials for Environmental Remediation., (2015) 93-112.
[65] H.H. Murray, Structure and composition of clay minerals and their physical and chemical properties. Development in clay Science., (2006) 7-31.
[66] A. M. Awad, M.R. Shaikh Shifa, M. H. Gulied, M. S. Nasser, A. Benamor, S. Adham, Adsorption of organic pollutants by natural and modified clays: A comprehensive review, Separation and Purification Technology, 228 (2019) e115719,
[67] A. Sales, F.R. de Souza, W.N. dos Santos, A. M. Zimer, F. do Couto Rosa Almeida, Lightweight composite concrete produced with water treatment sludge and sawdust: Thermal properties and potential application. Construction and Building Materials, 24 (12) (2010) 2446–2453.
[68] V. Krupskaya, L. Novikova, E. Tyupina, P. Belousov, O. Dorzhieva, S. Zakusin, K. Kim, L. Belchinskaya,  The influence of acid modification on the structure of montmorillonites and surface properties of bentonites. Applied Clay Science, 172 (2019) 1–10.
[69] Nicola, B.P., Bernardo-Gusmão, K., Schwanke, A.J. (2021). Smectite Clay Nanoarchitectures: Rational Design and Applications. In: Kharissova, O.V., Torres-Martínez, L.M., Kharisov, B.I. (eds) Handbook of Nanomaterials and Nanocomposites for Energy and Environmental Applications. Springer, Cham.   https://doi.org/10.1007/978-3-030-36268-3_60
[70] P. Komadel, Acid-activated clays: Materials in continuous demand. Applied Clay Science, 131, (2016) 84–99.
[71] Z. P. Tomic, V. P. Logar, B. M. Babic, J. R. Rogan,  & P. Makreski, Comparison of structural, textural, and thermal characteristics of pure and acid-treated bentonites from Aleksinac and Petrovac (Serbia). SpectrochimicaActa Part A: Molecular and Biomolecular Spectroscopy, 82(1), (2011)389–395
[72] G. Jozefaciuk, Effect of acid and alkali treatments on surface-charge properties of selected clay minerals. Clays and Clay Minerals, 50(5), (2002) 647–656.
[73] F. Hussin, M. K. Aroua, W. M. A. Daud, Textural characteristics, surface chemistry and activation of bleaching earth: A review. Chemical Engineering Journal, 170(1), (2011) 90–106.
[74] L. Chmielarz, M. Wojciechowska,  M. Rutkowska,  A. Adamski, A. WeRgrzyn,  A. Kowalczyk, A. Matusiewicz,  Acid-activated vermiculites as catalysts of the DeNOx process. Catalysis Today, 191(1) (2012)25–31.
[75] S. S. G. Santos, H. R. M. Silva, A. G. de Souza, A. P. M. Alves,  E. C. da Silva Filho, & M. G. Fonseca,  Acid-leached mixed vermiculites were obtained by treatment with nitric acid. Applied Clay Science, 104 (2015) 286–294.
[76] E. Ferrage, C.A. Kirk, G. Cressey, J. Cuadros, Dehydration of Ca-montmorillonite at the crystal scale. Part I: Structure evolution. 92(7), (2007) 994–1006
[77] K. Emmerich, F. T. Madsen, & G. Kahr, Dehydroxylation behavior of heat-treated and steam-treated homoionic cis-vacant montmorillonites. Clays and Clay Minerals, 47(5) (1999) 591–604.
[78] H. Chen, J. Zhao, A. Zhong, Y. Jin, Removal capacity and adsorption mechanism of heat-treated palygorskite clay for methylene blue. Chemical Engineering Journal, 174(1), (2011)143–150.
[79] H. Bayram, M. Önal, H. Yılmaz, and Y. Sarıkaya, Thermal analysis of white calcium bentonite. Journal of Thermal Analysis and Calorimetry, 101(3) (2010) 873-879
[80] A. Ardakani, M. Yazdani, The relation between particle density and static elastic moduli of lightweight expanded clay aggregates. Applied Clay Science, 93–94, (2014) 28–34.
[81] R. Bartolini, S. Filippozzi, E. Princi, C. Schenone, & S. Vicini, Acoustic and mechanical properties of expanded clay granulate consolidated by epoxy resin. Applied Clay Science, 48(3) (2010) 460–465.
[82] F. Lelario, M. IdoGardi Yael, D. Noam, U. Tomas, N. Shlomo S. Laura, A. Bufo Sabino,  Pairing micropollutants and clay-composite sorbents for efficient water treatment: filtration and modeling at a pilot scale. Appl Clay Sci 137(2017)225–232.
[83] A.V. Dordio, S. Miranda, J. P. Ramalho, & A. P. Carvalho, Mechanisms of removal of three widespread pharmaceuticals by two clay materials. Journal of Hazardous Materials, 323(2017) 575-583.
[84] K. Byorklund, L. Li, Evaluation of low-cost materials for sorption of hydrophobic organic pollutants in stormwater, J. Environ. Manage. 159(2015) 106–114.
[85] K. Styszko, K. Nosek, M. Motak, K. Bester, Preliminary selection of clay minerals for the removal of pharmaceuticals, bisphenol A and triclosan in acidic and neutral aqueous solutions, C. R. Chim., 18 (2015) 1134–1142.
[86] A.V. Dordio, A.J.E. Candeias, A.P. Pinto, C.T. Da Costa, A.J.P. Carvalho, Preliminary media screening for application in the removal of clofibric acid, carbamazepine, and ibuprofen by SSF-constructed wetlands, Ecol. Eng. 35 (2009)290–302.
[87] A.V. Dordio, J. Teimao, I. Ramalho, A.J.P. Carvalho, A.J.E. Candeias, Selection of a support matrix for the removal of some phenoxy acetic compounds in constructed wetlands systems, Sci. Total Environ. 380 (2007)237–246.
[88] L. Rafati, M.H. Ehrampoush, A.A. Rafati, Fixed bed adsorption column studies and models for removal of ibuprofen from aqueous solution by strong adsorbent Nano-clay composite. J Environ Health Sci Engineer, 17 (2019) 753–765
[89] H. Khazri, I. Ghorbel-Abid, R. Kalfat et al. Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study. Appl Water Sci, 7 (2017) 3031–3040
[90] R. Baccar, M. Sarra, J. Bouzid, M. Feki, P. Blanquez, Removal of pharmaceutical compounds by activated carbon prepared from the agricultural by-product. Chemical Engineering Journal, 211–212 (2012) 310–317.
[91] R. Khatem, R.O. Miguel, A. Bakhti: Use of synthetic clay for Removal of Diclofenac Anti-inflammatory. Eurasian Journal of Soil Science 4 (2) (2015) 126–136.
[92] R. Ghemit, A. Makhloufi, N. Djebri, A. Flilissa, L. Zerroual, M. Boutahala, Adsorptive removal of diclofenac and ibuprofen from aqueous solution by organobentonites: Study in single and binary systems, Groundwater for Sustainable Development, 8 (2019)520-529
[93] M. Barczak, M. Wierzbicka, P. Borowski. Sorption of diclofenac onto functionalized mesoporous silicas: Experimental and theoretical investigations, Microporous and Mesoporous Materials, Journal of hazardous materials 264 (2018) 254-264
[94] B.N. Bhadra, I. Ahmed, S. Kim, S.H. Jhung, Adsorptive removal of ibuprofen and diclofenac from water using metal-organic framework-derived porous carbon. Chem. Eng. J., 314 (2017) 50–58.
[95] H. Hiew, Y.Z. Bi, L.Y. Lee, K.C. Lai,  S. Gan,  S.T. Gopakumar, G.T. Pan, T.C.K. Yang, Adsorptive decontamination of diclofenac by three-dimensional graphene-based adsorbent: response surface methodology, adsorption equilibrium, kinetic and thermodynamic studies. Environ. Res., 168 (2019) 241–253.
[96]  M. Essandoh, B. Kunwar, C.U. Pittman Jr., D. Mohan, T. Mlsna, Sorptive removal of salicylic acid and ibuprofen from aqueous solutions using pine wood fast pyrolysis biochar. Chem. Eng. J. 265 (2015) 219–227.
[97] H. Nourmoradi, K.F. Moghadam, A. Jafari, B. Kama, Removal of acetaminophen and ibuprofen from aqueous solutions by activated carbon derived from quercusbrantii (oak) acorn as a low-cost biosorbent. Journal of Environmental Chemical Engineering 6 (6) (2018) 6807–6815.
[98] S. K. Behera, H.S. Park Sorptive removal of ibuprofen from water using selected soil minerals and activated carbon, Int. J. Environ. Sci. Technol., 9 (2012) 85–94
[99] T. Thiebault, M. Boussafir, L. Fougère , E. Destandau, L. Monnin, C. L. Milbeau ,Clay minerals for the removal of pharmaceuticals: Initial investigations of their adsorption properties in real wastewater effluents. Environmental Nanotechnology, Monitoring & Management, 12(2019) e100266
[100] M. Kryuchkova, S. Batasheva, F. Akhatova, V. Babaev, D. Buzyurova, A. Vikulina, D. Volodkin, R. Fakhrullin, E. Rozhina, Pharmaceuticals Removal by Adsorption with Montmorillonite Nanoclay. Int. J. Mol. Sci., 22, (2021) e9670.
[101] H. Khazri, I. Ghorbel-Abid, R. Kalfat, Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study. Appl Water Sci 7, (2017) 3031–3040. https://doi.org/10.1007/s13201-016-0414-3 
[102] R. Hadi, F. Fatola, M.A. Kenari, E. Eskandari, S. Ramakrishna, Selection of suitable bentonite and the influence of various acids on the preparation of a special clay for the removal of trace olefins from aromatics. Clay Minerals, 56(2021)(3) 185-196.
[103] A. Maged, J. Iqbal, S. Kharbish, I. Ismael, A. Bhatnagar, Tuning tetracycline removal from aqueous solution onto activated 2:1 layered clay mineral: characterization, sorption, and mechanistic studies, Journal of Hazardous Materials (2019)
[104] W. Zhang, Y. Ding, S.A. Boyd, B.J. Teppen, H. Li, Sorption and desorption of carbamazepine from water by smectite clays. Chemosphere 81, (2010) 954-960.
[105] R. Antón-Herrero, C. García-Delgado, M. Alonso-Izquierdo, G. García-Rodríguez, J. Cuevas, E. Eymar, Comparative adsorption of tetracyclines on biochars and stevensite: Looking for the most effective adsorbent. Appl. Clay Sci. 160, (2018) 162–172. 
[106] N. Genç, E. Can Dogan M. Yurtsever, Bentonite for ciprofloxacin removal from aqueous solution. Water Sci Technol,; 68(4)(2013) 848-55.
[107] V Arya, L. Philip. Adsorption of pharmaceuticals in water using Fe3O4 coated polymer clay composite, Microporous and Mesoporous Materials, Journal of hazardous materials., 232 (2016) 273-280
[108] Y. Wang, C. Shen, M. Zhang, B.T. Zhang, Y.G. Yu The electrochemical degradation of ciprofloxacin using a SnO2-Sb/Ti anode: influencing factors, reaction pathways, and energy demand. Chem Eng J., 296(2016) 79–89.
[109] Bui, T. X., Pham, V. H., Le, S. T., & Choi, H. Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15. Journal of hazardous materials, 254 (2013) 345-353.
[110] P.H. Chang, Z. Li, J.S. Jean, W.T. Jiang, C.J. Wang, K.H. Lin,  Adsorption of tetracycline on 2:1 layered non-swelling clay mineral illite. Appl. Clay Sci., 1563 (2012) 67–68
[111] H. Mabrouk, D.E. Akretche, Diclofenac potassium removal from water by adsorption on natural and pillared clay, Desalination and Water Treatment, (2016) 6033-6043
[112] A. Mittal, L. Kurup, V.K.  Gupta. Use of waste materials—Bottom Ash and De-Oiled Soya, as potential adsorbents for the removal of Amaranth from aqueous solutions, J. Hazard. Mater., 117(2005) 171–178.