The Potential of Gundelia Seeds Waste as an Emerging Sustainable Adsorbent for Methylene Blue-Polluted Water Treatment

Document Type : Original Article


1 Department of Chemical Engineering, College of Engineering, University of Baghdad, P.O. Box: 10071, Baghdad, Iraq

2 Department of Environmental Science, College of Energy and Environmental Science, Alkarkh University of Science, P.O. Box: 10081, Baghdad, Iraq


Gundelia, a genus of flowering plants native to the Mediterranean region, particularly in Iraq, holds promise as a sustainable adsorbent for the treatment of dye-polluted water. This study explores the potential of Gundelia seeds (GS) waste as a biobased adsorbent for removing methylene blue dye from synthesized wastewater. Utilizing various analytical techniques, including scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction analysis (XRD), we assessed GS as an active adsorbent with performance comparable to fabricated and expensive composites. Key parameters such as pH (3-11), pH at the point of zero charge, temperature (298-328 K), dose (0.02-0.1 g), dye concentration (10-50 ppm), and contact time (10-40 min) were systematically investigated. The point of zero charge was determined to be at pH 8, with the highest removal efficiency observed at pH 11. A contact time of 30 minutes yielded a removal rate of approximately 90 %, with an adsorption capacity of 11.07 mg/g. The highest adsorption capacity, 30.57 mg/g, was attained under conditions of 50 ppm dye concentration, 0.02 g dose, and a 40-minute contact time. The study examined three isotherm models, namely Langmuir, Freundlich, and Temkin; all demonstrating a high fit, with Langmuir exhibiting preferability. On the other hand, five kinetic models were explored; the Pseudo second-order model provided the most accurate description of the adsorption process.


Main Subjects

  1. Ahmed AU, Ibraheem H, Kadhom M, Rashad AA, Al-Dahhan WH, Bufaroosha M, et al. Modified PVC as adsorbent for methyl orange dye removable, 2022, p. 020006.
  2. Ismail Z, Go YI. Fog-to-Water for Water Scarcity in Climate-Change Hazards Hotspots: Pilot Study in Southeast Asia. Global Challenges 2021; 5. https://doi. org/10.1002/gch2.202000036.
  3. Droogers P, Immerzeel WW, Terink W, Hoogeveen J, Bierkens MFP, van Beek LPH, et al. Water resources trends in Middle East and North Africa towards 2050. Hydrol Earth Syst Sci. 2012; 16:3101-14. https://doi. org/10.5194/hess-16-3101-2012.
  4.                 Karadag D, Akgul E, Tok S, Erturk F, Kaya MA, Turan M. Basic and reactive dye removal using natural and modified zeolites. J Chem Eng Data. 2007; 52:2436-41.
  5. Silva F, Nascimento L, Brito M, da Silva K, Paschoal W, Fujiyama R. Biosorption of Methylene Blue Dye Using Natural Biosorbents Made from Weeds. Materials. 2019; 12:2486. 10.3390/ ma12152486.
  6. Küçükosmanoğlu M, Gezici O, Ayar A. The adsorption behaviors of Methylene Blue and Methyl Orange in a diaminoethane sporopollenin-mediated column system. Sep Purif Technol. 2006; 52:280-7. 1016/j.seppur.2006.05.005.
  7. Oladoye PO, Kadhom M, Khan I, Hama Aziz KH, Alli YA. Advancements in adsorption and photodegradation technologies for rhodamine B dye wastewater treatment: Fundamentals, applications, and future directions. Green Chem Eng. 2023; 1016/j.gce.2023.12.004.
  8.                 Salih SS, Mohammed HN, Abdullah GH, Kadhom M, Ghosh TK. Simultaneous removal of Cu(II), Cd(II), and industrial dye onto a composite chitosan biosorbent. J Polym Environ. 2020; 28:354-65. 1007/ s10924-019-01612-x.
  9. Salih SS, Mahdi A, Kadhom M, Ghosh TK. Competitive adsorption of As(III) and As(V) onto chitosan/diatomaceous earth adsorbent. J Environ Chem Eng. 2019; 7:103407. 2019.103407.
  10. Jawad AH, Kadhum AM, Ngoh YS. Applicability of dragon fruit (Hylocereus polyrhizus) peels as low-cost biosorbent for adsorption of methylene blue from aqueous solution: kinetics, equilibrium and thermodynamics studies. Desalination water treat 2018; 109:231-40.
  11. Adil H, Hussain Z, Kadhom M, Yousif E. Adsorptive removal of safranin-O dye from aqueous solutions using carrot seed, 2022, p. 040011. 10.1063/5.0121105.
  12. Salih SS, Kadhom M, Shihab MA, Ghosh TK. Competitive adsorption of Pb(II) and phenol onto modified chitosan/vermiculite adsorbents. J Polym Environ. 2022; 30:4238-51. s10924-022-02515-0.
  13. Boakye P, Ohemeng-Boahen G, Darkwah L, Sokama-Neuyam YA, Appiah-Effah E, Oduro-Kwarteng S, et al. Waste biomass and biomaterials adsorbents for wastewater treatment. Green Energy Enviro Technol. 2022; 2022:1–25.
  14. Moussavi G, Mahmoudi M. Removal of azo and anthraquinone reactive dyes from industrial wastewaters using MgO nanoparticles. J Hazard Mater. 2009;168:806-12. 2009. 02.097.
  15. Alalwan HA, Kadhom MA, Alminshid AH. Removal of heavy metals from wastewater using agricultural byproducts. J Water Supply: Res Technol-AQUA. 2020; 69:99-112. 2020. 133.
  16. Kadhom M, Albayati N, Alalwan H, Al-Furaiji M. Removal of dyes by agricultural waste. Sustain Chem Pharm. 2020; 16. 2020. 100259.
  17. Dalar A, Zengin G, Mukemre M, Bengu AS, İşler S. Gundelia rosea seed: Evaluation of biopharmaceutical potential and bioactive composition. South African J Botany. 2019; 125:505-10. sajb.2019.08.024.
  18. Hind N. 763. GUNDELIA TOURNEFORTII. Curtis’s Botanical Magazine 2013;30:114-38. 1111/curt.12027.
  19. Golshan Shandi S, Doulati Ardejani F, Sharifi F. Assessment of Cu (II) removal from an aqueous solution by raw Gundelia tournefortii as a new low-cost biosorbent: Experiments and modelling. Chin J Chem Eng. 2019; 27:1945-55. 2018.12.027.
  20. Rahimpour F, Shojaeimehr T, Sadeghi M. Biosorption of Pb(II) using Gundelia tournefortii : Kinetics, equilibrium, and thermodynamics. Sep Sci Technol. 2017; 52:596-607. 2016.1260140.
  21. Mokhtaryan S, Khodabakhshi A, Sadeghi R, Nourmoradi H, Shakeri K, Hemati S, et al. New activated carbon derived from Gundelia tournefortii seeds for effective removal of acetaminophen from aqueous solutions: Adsorption performance. Arabian J Chem. 2023; 16:105253. arabjc. 2023. 105253.
  22. Pezeshkvar T, Norouzi B, Moradian M, Mirabi A. Fabrication of new nanocomposites based on NiO-MWCNT-sodium dodecyl sulfate in the presence of Gundelia tournefortii extract: application for methanol electrooxidation in alkaline solution. J Solid State Electrochem. 2022; 26:1479-92. 1007/s10008-022-05182-2.
  23. Cwalinski T, Polom W, Marano L, Roviello G, D’Angelo A, Cwalina N, et al. Methylene Blue—Current Knowledge, Fluorescent Properties, and Its Future Use. J Clin Med. 2020; 9:3538. https://doi. org/10.3390/jcm9113538.
  24. Kadhom M, Kalash K, Al-Furaiji M. Performance of 2D MXene as an adsorbent for malachite green removal. Chemosphere. 2022; 290:133256. https://doi. org/10.1016/j.chemosphere.2021.133256.
  25. Ovchinnikov O V., Evtukhova A V., Kondratenko TS, Smirnov MS, Khokhlov VYu, Erina O V. Manifestation of intermolecular interactions in FTIR spectra of methylene blue molecules. Vib Spectrosc. 2016; 86:181-9. 2016. 06.016.
  26. Sartape AS, Mandhare AM, Jadhav VV., Raut PD, Anuse MA, Kolekar SS. Removal of malachite green dye from aqueous solution with adsorption technique using Limonia acidissima (wood apple) shell as low cost adsorbent. Arabian J Chem. 2017; 10:S3229-38.
  27. Kumar R, Ahmad R. Biosorption of hazardous crystal violet dye from aqueous solution onto treated ginger waste (TGW). Desalination. 2011; 265:112-8.
  28. [28]         Shamsipur M, Barati A, Nematifar Z. Fluorescent pH nanosensors: Design strategies and applications. J Photochem Photobiol C: Photochem Rev. 2019; 39:76-141. 03. 001.
  29. Bella F, Gerbaldi C, Barolo C, Grätzel M. Aqueous dye-sensitized solar cells. Chem Soc Rev. 2015; 44:3431-73.
  30. [30]         Alvarez-Silva M, Uribe-Salas A, Mirnezami M, Finch JA. The point of zero charge of phyllosilicate minerals using the Mular–Roberts titration technique. Miner Eng. 2010; 23:383-9. j.mineng.2009.11.013.
  31. Luo H, Liu Y, Lu H, Fang Q, Rong H. Efficient adsorption of tetracycline from aqueous solutions by modified alginate beads after the removal of Cu(II) Ions. ACS Omega. 2021; 6:6240-51. 1021/acsomega.0c05807.
  32. Silva F, Nascimento L, Brito M, da Silva K, Paschoal W, Fujiyama R. Biosorption of methylene blue dye using natural biosorbents made from weeds. Materials. 2019; 12:2486.
  33. Singh P, Sarswat A, Pittman CU, Mlsna T, Mohan D. Sustainable low-concentration arsenite [As(III)] removal in single and multicomponent systems using hybrid iron oxide–biochar nanocomposite adsorbents-a mechanistic study. ACS Omega. 2020; 5:2575-93.
  34. Muthukumaran C, Sivakumar VM, Thirumarimurugan M. Adsorption isotherms and kinetic studies of crystal violet dye removal from aqueous solution using surfactant modified magnetic nanoadsorbent. J Taiwan Inst Chem Eng. 2016; 63:354-62. 1016/ j.jtice.2016.03.034.
  35. S R, Lata S, P B. Biosorption characteristics of methylene blue and malachite green from simulated wastewater onto Carica papaya wood biosorbent. Surfaces Interfaces. 2018; 10:197-215. 10. 1016/j.surfin.2017.09.011.
  36. Zhou G, Wang KP, Liu HW, Wang L, Xiao XF, Dou DD, et al. Three-dimensional polylactic acid@ graphene oxide/chitosan sponge bionic filter: Highly efficient adsorption of crystal violet dye. Int J Biol Macromol. 2018; 113:792-803. 1016/ j.ijbiomac.2018.02.017.
  37. Boudrahem F, Aissani-Benissad F, Soualah A. Removal of basic yellow dye from aqueous solutions by sorption onto reed as an adsorbent. Desalination Water Treat. 2014:1-8. 19443994. 2014.888686.
  38. Jiang N, Shang R, Heijman SGJ, Rietveld LC. Adsorption of triclosan, trichlorophenol and phenol by high-silica zeolites: Adsorption efficiencies and mechanisms. Sep Purif Technol. 2020; 235:116152.
  39. Li L, Wang X, Zhang D, Guo R, Du X. Excellent adsorption of ultraviolet filters using silylated MCM-41 mesoporous materials as adsorbent. Appl Surf Sci. 2015; 328:26-33. 2014. 11.116.
  40. Foo KY, Hameed BH. Insights into the modeling of adsorption isotherm systems. Chem Eng J. 2010; 156:2-10.
  41. Vidal CB, Barros AL, Moura CP, de Lima ACA, Dias FS, Vasconcellos LuizCG, et al. Adsorption of polycyclic aromatic hydrocarbons from aqueous solutions by modified periodic mesoporous organosilica. J Colloid Interface Sci. 2011; 357:466-73.
  42. Kalash KR, Al-Furaiji MH, Waisi BI, Ali RA. Evaluation of adsorption performance of phenol using non-calcined Mobil composition of matter No. 41 particles. Desalination Water Treat. 2020; 198:232-40.
  43. Yang C. Statistical mechanical aspects of adsorption systems obeying the Temkin isotherm. J Phys Chem. 1993; 97:7097-101. 029.
  44. Sahoo TR, Prelot B. Adsorption processes for the removal of contaminants from wastewater. Nanomaterials for the detection and removal of wastewater pollutants. Elsevier; 2020, p. 161-222.
  45. Banerjee S, Chattopadhyaya MC, Uma, Sharma YC. Adsorption Characteristics of Modified Wheat Husk for the Removal of a Toxic Dye, Methylene Blue, from Aqueous Solutions. J Hazard Toxic Radioact Waste. 2014; 18:56-63. (ASCE) HZ. 2153-5515.0000191.
  46. ANNADURAI G, JUANG R, LEE D. Use of cellulose-based wastes for adsorption of dyes from aqueous solutions. J Hazard Mater. 2002; 92:263-74.
  47. Yavuz E, Bayramoğlu G, Arica MY, Senkal BF. Preparation of poly (acrylic acid) containing core-shell type resin for removal of basic dyes. J Chem Technol Biotechnol. 2011; 86:699-705. 1002/jctb.2571.
  48. Banerjee S, Dastidar MG. Use of jute processing wastes for treatment of wastewater contaminated with dye and other organics. Bioresour Technol. 2005; 96:1919-28. 01. 039.
  49. Han R, Wang Y, Han P, Shi J, Yang J, Lu Y. Removal of methylene blue from aqueous solution by chaff in batch mode. J Hazard Mater. 2006; 137:550-7.
  50. Bulut Y, Aydın H. A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. Desalination. 2006; 194:259-67. 1016/j.desal.2005.10.032.
  51. BATZIAS F, SIDIRAS D. Dye adsorption by calcium chloride treated beech sawdust in batch and fixed-bed systems. J Hazard Mater. 2004; 114:167-74.
  52. Franca AS, Oliveira LS, Ferreira ME. Kinetics and equilibrium studies of methylene blue adsorption by spent coffee grounds. Desalination. 2009; 249:267-72.
  53. Khattri SD, Singh MK. Colour removal from synthetic dye waste water using a bioadsorbent. Water Air Soil Pollut. 2000; 120:283-94. 1023/ A:1005207803041.
  54. Tsai WT, Hsu H-C, Su TY, Lin KY, Lin CM. Removal of basic dye (methylene blue) from wastewaters utilizing beer brewery waste. J Hazard Mater. 2008; 154:73-8. 2007. 09.107.