Environmental Science and Pollution Research

, Volume 26, Issue 19, pp 19615–19631 | Cite as

Efficient removal of p-nitrophenol from water using montmorillonite clay: insights into the adsorption mechanism, process optimization, and regeneration

  • Mahmoud El OuardiEmail author
  • Mohamed Laabd
  • Hicham Abou Oualid
  • Younes Brahmi
  • Abdelhadi Abaamrane
  • Abdelaziz Elouahli
  • Abdelaziz Ait Addi
  • Abdellatif Laknifli
Research Article


The present research highlights the use of a montmorillonite clay to remove p-nitrophenol (PNP) from aqueous solution. The montmorillonite clay was characterized using powder X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, X-ray fluorescence, Brunauer-Emmett-Teller analyses, and zero point charge in order to establish the adsorption behavior-properties relationship. The physiochemical parameters like pH, initial PNP concentration, and adsorbent dose as well as their binary interaction effects on the PNP adsorption yield were statistically optimized using response surface methodology. As a result, 99.5% removal of PNP was obtained under the optimal conditions of pH 2, adsorbent dose of 2 g/l, and PNP concentration of 20 mg/l. The interaction between adsorbent dose and initial concentration was the most influencing interaction on the PNP removal efficiency. The mass transfer of PNP at the solution/adsorbent interface was described using pseudo-first-order and intraparticle diffusion. Langmuir isotherm well fitted the experimental equilibrium data with a satisfactory maximum adsorption capacity of 122.09 mg/g. The PNP adsorption process was thermodynamically spontaneous and endothermic. The regeneration study showed that the montmorillonite clay exhibited an excellent recycling capability. Overall, the montmorillonite clay is very attractive as an efficient, low-cost, eco-friendly, and recyclable adsorbent for the remediation of hazardous phenolic compounds in industrial effluents.


p-Nitrophenol Adsorption Montmorillonite clay Response surface methodology Regeneration Water treatment 



We thank the Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR) for characterization techniques support.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2019_5219_MOESM1_ESM.doc (628 kb)
ESM 1 (DOC 628 kb)


  1. Aazza M, Ahlafi H, Moussout H, Maghat H (2017) Ortho-nitro-phenol adsorption onto alumina and surfactant modified alumina: kinetic, isotherm and mechanism. J Environ Chem Eng 5:3418–3428. CrossRefGoogle Scholar
  2. Abdelrasoul A, Doan H, Lohi A, Cheng CH (2017) The influence of aggregation of latex particles on membrane fouling attachments & ultrafiltration performance in ultrafiltration of latex contaminated water and wastewater. J Environ Sci 52:118–129. CrossRefGoogle Scholar
  3. Adeyemo AA, Adeoye IO, Bello OS (2017) Adsorption of dyes using different types of clay: a review. Appl Water Sci 7:543–568. CrossRefGoogle Scholar
  4. Ahmedzeki NS, Rashid HA, Alnaama AA, Alhasani MH, Abdulhussain Z (2013) Removal of 4-nitro-phenol from wastewater using synthetic zeolite and kaolin clay. Korean J Chem Eng 30:2213–2218. CrossRefGoogle Scholar
  5. Ait Ahsaine H, Zbair M, Anfar Z, Naciri Y, El haouti R, El Alem N, Ezahri M (2018) Cationic dyes adsorption onto high surface area “almond shell” activated carbon: kinetics, equilibrium isotherms and surface statistical modeling. Mater Today Chem 8:121–132. CrossRefGoogle Scholar
  6. Angar Y, Djelali NE, Kebbouche-Gana S (2017) Investigation of ammonium adsorption on Algerian natural bentonite. Environ Sci Pollut Res 24:11078–11089. CrossRefGoogle Scholar
  7. Bakas I, Elatmani K, Qourzal S, Barka N, Assabbane A, Ait-Ichou I (2014) A comparative adsorption for the removal of p-cresol from aqueous solution onto granular activated charcoal and granular activated alumina. J Mater Environ Sci 5:675–682Google Scholar
  8. Barka N, Bakas I, Qourzal S, Assabbane A, Ait-Ichou Y (2013) Degradation of phenol in water by titanium dioxide photocatalysis. Orient J Chem 29:1055–1060. CrossRefGoogle Scholar
  9. Bentahar Y, Hurel C, Draoui K, Khairoun S, Marmier N (2016) Adsorptive properties of Moroccan clays for the removal of arsenic(V) from aqueous solution. Appl Clay Sci 119:385–392. CrossRefGoogle Scholar
  10. Box GE, Hunter JS (1957) Multi-factor experimental designs for exploring response surfaces. Ann Math Stat 28:195–241. CrossRefGoogle Scholar
  11. Cairns A, Yarker YE (2008) The role of healthcare communications agencies in maintaining compliance when working with the pharmaceutical industry and healthcare professionals. Curr Med Res Opin 24:1371–1378. CrossRefGoogle Scholar
  12. Chicinaş RP, Bedelean H, Stefan R, Măicăneanu A (2018) Ability of a montmorillonitic clay to interact with cationic and anionic dyes in aqueous solutions. J Mol Struct 1154:187–195. CrossRefGoogle Scholar
  13. Churchman GJ, Gates WP, Theng BKG, Yuan G (2006) In: Bergaya F, Theng BKG, Lagaly G (Eds.), Clays and clay minerals for pollution control, Development in clay science, vol. 1, Elsevier Press.
  14. El-Said GF, El-Sadaawy MM, Aly-Eldeen MA (2018) Adsorption isotherms and kinetic studies for the defluoridation from aqueous solution using eco-friendly raw marine green algae, Ulva lactuca. Environ Monit Assess 190:1-15.
  15. Ely A, Baudu M, Basly JP, Kankou MOSAO (2009) Copper and nitrophenol pollutants removal by Na-montmorillonite/alginate microcapsules. J Hazard Mater 171:405–409. CrossRefGoogle Scholar
  16. Ely A, Baudu M, Kankou MOSAO, Basly JP (2011) Copper and nitrophenol removal by low cost alginate/Mauritanian clay composite beads. Chem Eng J 178:168–174. CrossRefGoogle Scholar
  17. Erdem M, Yüksel E, Tay T, Çimen Y, Türk H (2009) Synthesis of novel methacrylate based adsorbents and their sorptive properties towards p-nitrophenol from aqueous solutions. J Colloid Interface Sci 333:40–48. CrossRefGoogle Scholar
  18. Fisal A, Daud WMAW, Ahmad MA, Radzi R (2011) Using cocoa (Theobroma cacao) shell-based activated carbon to remove 4-nitrophenol from aqueous solution: kinetics and equilibrium studies. Chem Eng J 178:461–467. CrossRefGoogle Scholar
  19. Frisch MJ et al. (2009) GAUSSIAN 09, Rev. D.01, Gaussian, Inc., Wallingford, CT.Google Scholar
  20. Gao T, Chen H, Xia S, Zhou Z (2008) Review of water pollution control in China. Front Environ Sci Eng China 2:142–149. CrossRefGoogle Scholar
  21. Ghorbel-Abid I, Galai K, Trabelsi-Ayadi M (2010) Retention of chromium (III) and cadmium (II) from aqueous solution by illitic clay as a low-cost adsorbent. Desalination 256:190–195. CrossRefGoogle Scholar
  22. Gusmão KAG, Gurgel LVA, Melo TMS, Gil LF (2013) Adsorption studies of methylene blue and gentian violet on sugarcane bagasse modified with EDTA dianhydride (EDTAD) in aqueous solutions: kinetic and equilibrium aspects. J Environ Manage 118:135–143. CrossRefGoogle Scholar
  23. Hadjltaief HB, Da Costa P, Beaunier P, Gálvez ME, Ben Zina M (2014) Fe-clay-plate as a heterogeneous catalyst in photo-Fenton oxidation of phenol as probe molecule for water treatment. Appl Clay Sci 91:46–54. CrossRefGoogle Scholar
  24. Ho Y (2006) Review of second-order models for adsorption systems. J Hazard Mater 136:681–689. CrossRefGoogle Scholar
  25. Hu J, Tan X, Ren X, Wang X (2012) Effect of humic acid on nickel (II) sorption to Ca-montmorillonite by batch and EXAFS techniques study. Dalton Trans 41:10803–10810. CrossRefGoogle Scholar
  26. Jaerger S, dos Santos A, Fernandes AN, Almeida CAP (2015) Removal of p-nitrophenol from aqueous solution using Brazilian peat: kinetic and thermodynamic studies. Water Air Soil Pollut 226:236. CrossRefGoogle Scholar
  27. Jung KW, Kim DH, Kim HW, Shin HS (2011) Optimization of combined (acid + thermal) pretreatment for fermentative hydrogen production from Laminaria japonica using response surface methodology (RSM). Int J Hydrog Energy 36:9626–9631. CrossRefGoogle Scholar
  28. Kadam HK, Tilve SG (2015) Advancement in methodologies for reduction of nitroarenes. RSC Adv 5(101):83391–83407. CrossRefGoogle Scholar
  29. Kara M, Yuzer H, Sabah E, Celik MS (2003) Adsorption of cobalt from aqueous solutions onto sepiolite. Water Res 37:224–232. CrossRefGoogle Scholar
  30. Kasiri M, Khataee A (2012) Removal of organic dyes by UV/H2O2 process: modelling and optimization. Environ Technol 33:1417–1425. CrossRefGoogle Scholar
  31. Kausar A, Iqbal M, Javed A, Aftab K, Bhatti HN, Nouren S (2018) Dyes adsorption using clay and modified clay: a review. J Mol Liq 256:395–407. CrossRefGoogle Scholar
  32. Kim KH, Jahan SA, Kabir E (2013) A review on human health perspective of air pollution with respect to allergies and asthma. Environ Int 59:41–52. CrossRefGoogle Scholar
  33. Laabd M, El Jaouhari A, Bazzaoui M, Albourine A, El Jazouli H (2017) Adsorption of benzene-polycarboxylic acids on the electrosynthesized polyaniline films: experimental and DFT calculation. J Polym Environ 25:359–369. CrossRefGoogle Scholar
  34. Lagergren S (1898) Zur theorie der sogenannten adsorption geloster stoffe kungliga svenska vetenskapsakademiens. Handlingar 24:1–39Google Scholar
  35. Lazo-Cannata JC, Nieto-Márquez A, Jacoby A, Paredes-Doig AL, Romero A, Sun-Kou MR, Valverde JL (2011) Adsorption of phenol and nitrophenols by carbon nanospheres: effect of pH and ionic strength. Sep Purif Technol 80:217–224. CrossRefGoogle Scholar
  36. Lee SY, Choi HJ (2018) Persimmon leaf bio-waste for adsorptive removal of heavy metals from aqueous solution. J Environ Manage 209:382–392. CrossRefGoogle Scholar
  37. Leite AB, Saucier C, Lima EC, dos Reis GS, Umpierres CS, Mello BL, Shirmardi M, Dias SLP, Sampaio CH (2018) Activated carbons from avocado seed: optimisation and application for removal of several emerging organic compounds. Environ Sci Pollut Res 25:7647-7661.
  38. Li C, Wang X, Meng D, Zhou L (2018) Facile synthesis of low-cost magnetic biosorbent from peach gum polysaccharide for selective and efficient removal of cationic dyes. Int J Biol Macromol 107:1871–1878. CrossRefGoogle Scholar
  39. Liu HL, Chiou YR (2005) Optimal decolorization efficiency of Reactive Red 239 by UV/TiO2 photocatalytic process coupled with response surface methodology. Chem Eng J 112:173–179. CrossRefGoogle Scholar
  40. Liu M, Li X, Du Y, Han R (2018) Adsorption of methyl blue from solution using walnut shell and reuse in a secondary adsorption for Congo red. Bioresour Technol Rep (In Press)
  41. Maghami M, Abdelrasoul A (2018) Zeolites-mixed-matrix nanofiltration membranes for the next generation of water purification. IntechOpen (In Press).
  42. Maisonet M, Correa A, Misra D, Jaakkola JJK (2004) A review of the literature on the effects of ambient air pollution on fetal growth. Environ Res 95:106–115. CrossRefGoogle Scholar
  43. Markus J, McBratney AB (2001) A review of the contamination of soil with lead II. Spatial distribution and risk assessment of soil lead. Environ Int 27:399–411. CrossRefGoogle Scholar
  44. Milonjić SK (2007) A consideration of the correct calculation of thermodynamic parameters of adsorption. J Serb Chem Soc 72:1363–1367CrossRefGoogle Scholar
  45. Nabbou N, Belhachemi M, Boumelik M, Merzougui T, Lahcene D, Harek Y, Zorpas AA, Jeguirim M (2018) Removal of fluoride from groundwater using natural clay (kaolinite): optimization of adsorption conditions. CR Chim (In Press) 22:105-112
  46. Ngulube T, Gumbo JR, Masindi V, Maity A (2018) An update on synthetic dyes adsorption onto clay based minerals: a state-of-art review. J Environ Manage 191:35–57. CrossRefGoogle Scholar
  47. Ofomaja AE (2011) Kinetics and pseudo-isotherm studies of 4-nitrophenol adsorption onto mansonia wood sawdust. Ind Crop Prod 33:418–428. CrossRefGoogle Scholar
  48. Ofomaja AE, Unuabonah EI (2013) Kinetics and time-dependent Langmuir modeling of 4-nitrophenol adsorption onto Mansonia sawdust. J Taiwan Inst Chem Eng 44:566–576. CrossRefGoogle Scholar
  49. Ouachtak H, Akhouairi S, Ait Addi A, Ait Akbour R, Jada A, Douch J, Hamdani M (2018) Mobility and retention of phenolic acids through a goethite-coated quartz sand column. Colloids Surf A 546:9–19. CrossRefGoogle Scholar
  50. Peng K, Fu L, Yang H, Ouyang J (2016) Perovskite LaFeO3/montmorillonite nanocomposites: synthesis, interface characteristics and enhanced photocatalytic activity. Sci Rep 6:19723. CrossRefGoogle Scholar
  51. Pham TH, Lee BK, Kim J (2016) Improved adsorption properties of a nano zeolite adsorbent toward toxic nitrophenols. Process Saf Environ Prot 104:314–322. CrossRefGoogle Scholar
  52. Prahas D, Kartika Y, Indraswati N, Ismadji S (2008) Activated carbon from jackfruit peel waste by H3PO4 chemical activation: pore structure and surface chemistry characterization. Chem Eng J 140:32–42. CrossRefGoogle Scholar
  53. Praveen Kumar S, Munusamy S, Muthamizh S, Padmanaban A, Dhanasekaran T, Gnanamoorthy G, Narayanan V (2018) Voltammertic determination of 4-nitrophenol by N,N′-bis(salicylaldimine)-benzene-1,2-diamine manganese(II) Schiff base complex modified GCE. Materials Today: Proceedings, 5:8973-8980.
  54. Qourzal S, Barka N, Belmouden M, Abaamrane A, Alahiane S, Elouardi M, Assabbane A, Ait-Ichou Y (2012) Heterogeneous photocatalytic degradation of 4-nitrophenol on suspended titania surface in a dynamic photoreactor. Fresenius Environ Bull 21:1972–1981Google Scholar
  55. Rodrigues CSD, Borges RAC, Lima VN, Madeira LM (2018a) p-Nitrophenol degradation by Fenton’s oxidation in a bubble column reactor. J Environ Manage 206:774–785. CrossRefGoogle Scholar
  56. Rodrigues DAS, Moura JM, Dotto GL, Cadaval TRS Jr, Pinto LAA (2018b) Preparation, characterization and dye adsorption/reuse of chitosan-vanadate films. J Polym Environ 26:2917. CrossRefGoogle Scholar
  57. Sennour R, Mimane G, Benghalem A, Taleb S (2009) Removal of the persistent pollutant chlorobenzene by adsorption onto activated montmorillonite. Appl Clay Sci 43:503–506. CrossRefGoogle Scholar
  58. Shaban M, Abukhadra MR, Shahien MG, Ibrahim SS (2018) Novel bentonite/zeolite-NaP composite efficiently removes methylene blue and Congo red dyes. Environ Chem Lett 16:275–280. CrossRefGoogle Scholar
  59. Shen XE, Shan XQ, Dong DM, Hua XY, Owens G (2009) Kinetics and thermodynamics of sorption of nitroaromatic compounds to as-grown and oxidized multiwalled carbon nanotubes. J Colloid Interface Sci 330:1–8. CrossRefGoogle Scholar
  60. Sing KSW (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl Chem 57:603–619. CrossRefGoogle Scholar
  61. Stanković N, Logar M, Luković J, Pantić J, Miljević M, Babić B, Radosavljević-Mihajlović A (2011) Characterization of bentonite clay from ‘Greda’ deposit, Process. Appl Ceram 5:97–101. CrossRefGoogle Scholar
  62. Subbaiah MV, Kim DS (2016) Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder: kinetics, isotherms, and thermodynamic studies. Ecotoxicol Environ Saf 128:109–117. CrossRefGoogle Scholar
  63. Tomar SK, Chakraborty S (2018) Effect of air flow rate on development of aerobic granules, biomass activity and nitrification efficiency for treating phenol, thiocyanate and ammonium. J Environ Manage 219:178–188. CrossRefGoogle Scholar
  64. Uddin MK (2017) A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade. Chem Eng J 308:438–462. CrossRefGoogle Scholar
  65. Vikas M, Dwarakish GS (2015) Coastal pollution: a review. Aquat Procedia 4:381–388. CrossRefGoogle Scholar
  66. Wong S, Ngadi N, Inuwa IM, Hassan O (2018) Recent advances in applications of activated carbon from biowaste for wastewater treatment: a short review. J Cleaner Prod 175:361–375. CrossRefGoogle Scholar
  67. Xue G, Gao M, Gu Z, Luo Z, Hu Z (2013) The removal of p-nitrophenol from aqueous solutions by adsorption using gemini surfactants modified montmorillonites. Chem Eng J 218:223–231. CrossRefGoogle Scholar
  68. Yang W, Yu Z, Pan B, Lv L, Zhang W (2015) Simultaneous organic/inorganic removal from water using a new nanocomposite adsorbent: a case study of p-nitrophenol and phosphate. Chem Eng J 268:399–407. CrossRefGoogle Scholar
  69. Yang J, Pan B, Li H, Liao S, Zhang D, Wu M, Xing B (2016) Degradation of p-nitrophenol on biochars: role of persistent free radicals. Environ Sci Technol 50:694–700. CrossRefGoogle Scholar
  70. Zbair M, Ahsaine HA, Anfar Z (2018) Porous carbon by microwave assisted pyrolysis: an effective and low-cost adsorbent for sulfamethoxazole adsorption and optimization using response surface methodology. J Cleaner Prod 202:571–581. CrossRefGoogle Scholar
  71. Zbair M, Anfar Z, Ahsaine HA (2019) Reusable bentonite clay: modelling and optimization of hazardous lead and p-nitrophenol adsorption using a response surface methodology approach. RSC Adv. 9:5756–5769. CrossRefGoogle Scholar
  72. Zeng A, Zeng A (2017) Synthesis of a quaternized beta cyclodextrin-montmorillonite composite and its adsorption capacity for Cr(VI), methyl orange, and p-nitrophenol. Water Air Soil Pollut 228:278–295. CrossRefGoogle Scholar
  73. Zhang QA, Zhang ZQ, Yue XF, Fan XH, Li T, Chen SF (2009) Response surface optimization of ultrasound-assisted oil extraction from autoclaved almond powder. Food Chem 116:513–518. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Mahmoud El Ouardi
    • 1
    • 2
    Email author
  • Mohamed Laabd
    • 3
  • Hicham Abou Oualid
    • 4
  • Younes Brahmi
    • 5
  • Abdelhadi Abaamrane
    • 6
  • Abdelaziz Elouahli
    • 7
  • Abdelaziz Ait Addi
    • 8
  • Abdellatif Laknifli
    • 1
  1. 1.Laboratory of Biotechnology, Materials and Environment, Faculty of SciencesIbn Zohr UniversityAgadirMorocco
  2. 2.University Campus of Ait MelloulIbn Zohr UniversityAgadirMorocco
  3. 3.Laboratory of Materials and Environment, Faculty of SciencesIbn Zohr UniversityAgadirMorocco
  4. 4.Faculty of Sciences and TechnologiesMohammedia, University of Hassan IICasablancaMorocco
  5. 5.Materials Science and Nanoengineering DepartmentMohamed VI Polytechnic UniversityBenguerirMorocco
  6. 6.Faculty of ScienceIbn Zohr UniversityAgadirMorocco
  7. 7.Biomaterials and Electrochemistry Team, Faculty of ScienceChouaib Doukkali UniversityEl JadidaMorocco
  8. 8.Physical Chemistry and Environment Team, Faculty of ScienceIbn Zohr UniversityAgadirMorocco

Personalised recommendations