Isothermal Modeling and MOORA-Guided Model Selection for Hexavalent Chromium Adsorption on a Sugarcane Bagasse–Lemongrass Blend
DOI:
https://doi.org/10.54987/jemat.v12i2.1115Keywords:
Chromium (VI) adsorption, Sugarcane bagasse–lemongrass blend, Isothermal modeling, Nonlinear regression, MOORA rankingAbstract
Chromium toxicity, present at elevated levels, poses a challenge for its remediation. The use of agricultural spent biomass as an adsorbent is one of the best mitigation efforts to date. This study investigates the adsorption of hexavalent chromium ions (Cr(VI)) onto Sugarcane Bagasse–Lemongrass Blend, and employs nonlinear regression to evaluate several isothermal models. The performance of the models was assessed using multiple error functions. While most models showed good fits, the Koble-Carrigan, Henry, and Dubinin–Radushkevich models showed poor convergence or high error. The Multiobjective Optimization on the Basis of Ratio Analysis (MOORA) method was employed for model ranking, as the error function analysis yielded inconsistent results. MOORA indicated that the Toth, Freundlich, and Fritz–Schlunder III models were the top performers. The Toth model calculated the maximum adsorption capacity of qmT of 0.91 mg/g, which is slightly lower than the experimental maximum of 1.21 mg/g. The Toth exponent nT = 0.72 value is closer to unity, suggesting a relatively homogeneous surface with adsorption behavior that resembles the Langmuir model. Despite robust modeling, the limited dataset introduces uncertainty in parameter estimation, underscoring the need for larger datasets. This study also emphasizes MOORA's potential in adsorption science as an efficient multi-criteria model selection tool.
References
Tumolo M, Ancona V, De Paola D, Losacco D, Campanale C, Massarelli C, et al. Chromium Pollution in European Water, Sources, Health Risk, and Remediation Strategies: An Overview. International Journal of Environmental Research and Public Health. 2020 Jan;17(15):5438.
Prasad S, Yadav KK, Kumar S, Gupta N, Cabral-Pinto MMS, Rezania S, et al. Chromium contamination and effect on environmental health and its remediation: A sustainable approaches. Journal of Environmental Management. 2021 May 1;285:112174.
Mohammadpour A, Gharehchahi E, Gharaghani MA, Shahsavani E, Golaki M, Berndtsson R, et al. Assessment of drinking water quality and identifying pollution sources in a chromite mining region. Journal of Hazardous Materials. 2024 Dec 5;480:136050.
Chaudhuri M, Azizan NKB. Adsorptive Removal of Chromium(VI) from Aqueous Solution by an Agricultural Waste-Based Activated Carbon. Water Air Soil Pollut. 2012 May 1;223(4):1765-71.
Amir A, Rahim R, Abdul-Talib S. Removal of Chromium Hexavalent Using Agriculture Waste. International Journal of Environmental Science and Development. 2017 Jan 1;8:260-3.
Hanafiah SFM, Salleh NFM, Ghafar NA, Shukri NM, Kamarudin NHN, Hapani M, et al. Efficiency of Coconut Husk as Agricultural Adsorbent in Removal of Chromium and Nickel Ions from Aqueous Solution. IOP Conf Ser: Earth Environ Sci. 2020 Dec;596(1):012048.
Konradt N, Dillmann S, Becker J, Schroden D, Rohns HP, Wagner C, et al. Removal of Chromium Species from Low-Contaminated Raw Water by Different Drinking Water Treatment Processes. Water. 2023 Jan;15(3):516.
Singh VP, Godara P, Srivastava A. Sustainable microalgal bioremediation of heavy metals and dyes from synthetic wastewater: Progressing towards United Nations Sustainable Development Goals. Waste Management Bulletin. 2024 Dec 1;2(4):123-35.
Meftah S, Meftah K, Drissi M, Radah I, Malous K, Amahrous A, et al. Heavy metal polluted water: Effects and sustainable treatment solutions using bio-adsorbents aligned with the SDGs. Discov Sustain. 2025 Feb 25;6(1):137.
Foo LPY, Tee CZ, Raimy NR, Hassell DG, Lee LY. Potential Malaysia agricultural waste materials for the biosorption of cadmium(II) from aqueous solution. Clean Techn Environ Policy. 2012 Apr 1;14(2):273-80.
Khan T, Isa MH, Mustafa MRU, Yeek-Chia H, Baloo L, Manan TSBA, et al. Cr(VI) adsorption from aqueous solution by an agricultural waste based carbon. RSC Adv. 2016 June 9;6(61):56365-74.
Khalifa MAS, Malek NANN, Farimani AY, Sani NS, Kamaru AA. Cetylpyridinium bromide (CPB)-treated sugarcane bagasse for the removal of chromate in aqueous solution. Materials Today: Proceedings. 2021 Jan 1;47:1252-7.
Aminu Dangamba S, Oyegoke T, Ocheje F, Aminu Dikko M, Galadima M. Evaluating the Adsorption Potential of Sugarcane Bagasse and Lemongrass for Chromium (VI) Removal in Wastewater Treatment. Journal of Engineering Science. 2024 Nov 20;31:96-116.
Garg UK, Kaur MP, Garg VK, Sud D. Removal of hexavalent chromium from aqueous solution by agricultural waste biomass. J Hazard Mater. 2007 Feb 9;140(1-2):60-8.
Vijayaraghavan K, Joshi UM, Balasubramanian R. Removal of metal ions from storm-water runoff by low-cost sorbents: Batch and column studies. Journal of Environmental Engineering. 2010;136(10):1113-8.
Mesfin Yeneneh A, Maitra S, Eldemerdash U. Study on biosorption of heavy metals by modified lignocellulosic waste. Journal of Applied Sciences. 2011;11(21):3555-62.
Dos Santos VCG, Salvado ADPA, Dragunski DC, Peraro DNC, Tarley CRT, Caetano J. Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments. Quimica Nova. 2012;35(8):1606-11.
Ullah I, Nadeem R, Iqbal M, Manzoor Q. Biosorption of chromium onto native and immobilized sugarcane bagasse waste biomass. Ecological Engineering. 2013;60:99-107.
Sadaf S, Bhatti HN, Nausheen S, Noreen S. Potential use of low-cost lignocellulosic waste for the removal of direct violet 51 from aqueous solution: Equilibrium and breakthrough studies. Archives of Environmental Contamination and Toxicology. 2014;66(4):557-71.
Mahmood-ul-Hassan M, Suthar V, Rafique E, Ahmad R, Yasin M. Kinetics of cadmium, chromium, and lead sorption onto chemically modified sugarcane bagasse and wheat straw. Environ Monit Assess. 2015 June 27;187(7):470.
Tawfik GM, Dila KAS, Mohamed MYF, Tam DNH, Kien ND, Ahmed AM, et al. A step by step guide for conducting a systematic review and meta-analysis with simulation data. Tropical Medicine and Health. 2019 Aug 1;47(1):46.
Khare KS, Phelan FR. Quantitative Comparison of Atomistic Simulations with Experiment for a Cross-Linked Epoxy: A Specific Volume-Cooling Rate Analysis. Macromolecules. 2018;51(2):564-75.
Langmuir I. THE ADSORPTION OF GASES ON PLANE SURFACES OF GLASS, MICA AND PLATINUM. Journal of the American Chemical Society. 1918;40(2):1361-402.
Schirmer W. Physical Chemistry of Surfaces. Zeitschrift für Physikalische Chemie. 1999;210(1):134-5.
Ridha FN, Webley PA. Anomalous Henry's law behavior of nitrogen and carbon dioxide adsorption on alkali-exchanged chabazite zeolites. Separation and Purification Technology. 2009;67(3):336-43.
Jovanovi? DS. Physical adsorption of gases - I: Isotherms for monolayer and multilayer adsorption. Kolloid-Zeitschrift & Zeitschrift für Polymere. 1969;235(1):1203-13.
Carmo AM, Hundal LS, Thompson ML. Sorption of hydrophobic organic compounds by soil materials: Application of unit equivalent Freundlich coefficients. Environmental Science and Technology. 2000;34(20):4363-9.
Radushkevich LV. Potential theory of sorption and structure of carbons. Zhurnal Fizicheskoi Khimii. 1949;23:1410-20.
Dubinin MM. Modern state of the theory of volume filling of micropore adsorbents during adsorption of gases and steams on carbon adsorbents. Zh Fiz Khim. 1965;39(6):1305-17.
Mahanty B, Behera SK, Sahoo NK. Misinterpretation of Dubinin-Radushkevich isotherm and its implications on adsorption parameter estimates. Separation Science and Technology. 2023 May 3;58(7):1275-82.
Mudhoo A, Pittman CU. The Dubinin-Radushkevich models: Dissecting the ps/p to cs/ce replacement in solid-aqueous interfacial adsorption and tracking the validity of E = 8 kJ mol-1 for assigning sorption type. Chemical Engineering Research and Design. 2023 Oct 1;198:370-402.
Koble RA, Corrigan TE. Adsorption isotherms for pure hydrocarbons. Ind Eng Chem. 1952 Feb 1;44(2):383-7.
Temkin MI, Pyzhev V. Kinetics of ammonia synthesis on promoted iron catalysts. Acta Physicochim USSR. 1940;12(3):327-56.
Chu KH. Revisiting the Temkin Isotherm: Dimensional Inconsistency and Approximate Forms. Industrial & Engineering Chemistry Research [Internet]. 2021 Aug 16 [cited 2022 Sept 1]; Available from: https://pubs.acs.org/doi/pdf/10.1021/acs.iecr.1c01788
Redlich O, Peterson DL. A Useful Adsorption Isotherm. Shell Development Company, Emeryville, California. 1958;63:1024.
Sips R. On the structure of a catalyst surface. The Journal of Chemical Physics. 1948;16(5):490-5.
Tóth J. Uniform interpretation of gas/solid adsorption. Advances in Colloid and Interface Science. 1995;55(C):1-239.
Hill AV. The possible effects of the aggregation of the molecules of haemoglobin on its dissociation curves. J Physiol. 1910;40:iv-vii.
Khan AA, Singh RP. Adsorption thermodynamics of carbofuran on Sn (IV) arsenosilicate in H+, Na+ and Ca2+ forms. Colloids and Surfaces. 1987;24(1):33-42.
Brunauer S, Emmett PH, Teller E. Adsorption of Gases in Multimolecular Layers. Journal of the American Chemical Society. 1938;60(2):309-19.
Vieth WR, Sladek KJ. A model for diffusion in a glassy polymer. Journal of Colloid Science. 1965;20(9):1014-33.
Radke CJ, Prausnitz JM. Adsorption of Organic Solutes from Dilute Aqueous Solution of Activated Carbon. Journal of the American Chemical Society. 1972;11(4):445-51.
Liu Y, Liu YJ. Biosorption isotherms, kinetics and thermodynamics. Separation and Purification Technology. 2008;61(3):229-42.
Tran HN, Bollinger JC, Lima EC, Juang RS. How to avoid mistakes in treating adsorption isotherm data (liquid and solid phases): Some comments about correctly using Radke-Prausnitz nonlinear model and Langmuir equilibrium constant. J Environ Manage. 2023 Jan 1;325(Pt A):116475.
Brouers F, Sotolongo O, Marquez F, Pirard JP. Microporous and heterogeneous surface adsorption isotherms arising from Levy distributions. Physica A: Statistical Mechanics and its Applications. 2005 Apr 1;349(1):271-82.
Hamissa AMB, Brouers F, Mahjoub B, Seffen M. Adsorption of Textile Dyes Using Agave Americana (L.) Fibres: Equilibrium and Kinetics Modelling. Adsorption Science & Technology. 2007 June 1;25(5):311-25.
Brouers F, Al-Musawi TJ. Brouers-Sotolongo fractal kinetics versus fractional derivative kinetics: A new strategy to analyze the pollutants sorption kinetics in porous materials. Journal of Hazardous Materials. 2018 May 15;350:162-8.
Fritz W, Schluender EU. Simultaneous adsorption equilibria of organic solutes in dilute aqueous solutions on activated carbon. Chemical Engineering Science. 1974;29(5):1279-82.
Chu KH, Tan B. Is the Frumkin (Fowler-Guggenheim) adsorption isotherm a two- or three-parameter equation? Colloid and Interface Science Communications. 2021 Nov 1;45:100519.
Martucci A, Braschi I, Bisio C, Sarti E, Rodeghero E, Bagatin R, et al. Influence of water on the retention of methyl tertiary-butyl ether by high silica ZSM-5 and Y zeolites: A multidisciplinary study on the adsorption from liquid and gas phase. RSC Advances. 2015;5(106):86997-7006.
Chu KH, Debord J, Harel M, Bollinger JC. Mirror, Mirror on the Wall, Which Is the Fairest of Them All? Comparing the Hill, Sips, Koble-Corrigan, and Liu Adsorption Isotherms. Ind Eng Chem Res. 2022 May 18;61(19):6781-90.
Shukor MY. Chitosan-Silica Composite Aerogel for the Adsorption of Cupric Ions: Isothermal Remodeling and MOORA-Based Model Selection. Journal of Environmental Microbiology and Toxicology. 2024 Dec 26;12(2):53-62.
Hannan EJ, Quinn BG. The Determination of the Order of an Autoregression. Journal of the Royal Statistical Society: Series B (Methodological). 1979;41(2):190-5.
Ross T. Indices for performance evaluation of predictive models in food microbiology. Journal of Applied Bacteriology. 1996;81(5):501-8.
Ezekiel M. The Sampling Variability of Linear and Curvilinear Regressions: A First Approximation to the Reliability of the Results Secured by the Graphic 'Successive Approximation' Method. The Annals of Mathematical Statistics. 1930;1(4):275-333.
Akaike H. A New Look at the Statistical Model Identification. IEEE Transactions on Automatic Control. 1974;19(6):716-23.
Burnham KP, Anderson DR. Multimodel inference: Understanding AIC and BIC in model selection. Sociological Methods and Research. 2004;33(2):261-304.
Marquardt DW. An Algorithm for Least-Squares Estimation of Nonlinear Parameters. Journal of the Society for Industrial and Applied Mathematics. 1963;11(2):431-41.
Seidel A, Gelbin D. On applying the ideal adsorbed solution theory to multicomponent adsorption equilibria of dissolved organic components on activated carbon. Chemical Engineering Science. 1988 Jan 1;43(1):79-88.
Porter JF, McKay G, Choy KH. The prediction of sorption from a binary mixture of acidic dyes using single- and mixed-isotherm variants of the ideal adsorbed solute theory. Chemical Engineering Science. 1999;54(24):5863-85.
Schwarz G. Estimating the Dimension of a Model. The Annals of Statistics. 1978;6(2):461-4.
Motulsky HJ, Ransnas LA. Fitting curves to data using nonlinear regression: a practical and nonmathematical review. The FASEB Journal. 1987;1(5):365-74.
Prasanthi MR, Jayasravanthi M, Nadh RV. Kinetic, thermodynamic and equilibrium studies on removal of hexavalent chromium from aqueous solutions using agro-waste biomaterials, casuarina equisetifolia L. and sorghum bicolor. Korean Journal of Chemical Engineering. 2016;33(8):2374-83.
Rzig B, Guesmi F, Sillanpää M, Hamrouni B. Biosorption potential of olive leaves as a novel low-cost adsorbent for the removal of hexavalent chromium from wastewater. Biomass Conv Bioref. 2024 June 1;14(12):12961-79.
Ayele AL, Tizazu BZ, Wassie AB. Chemical Modification of Teff Straw Biomass for Adsorptive Removal of Cr (VI) from Aqueous Solution: Characterization, Optimization, Kinetics, and Thermodynamic Aspects. Adsorption Science & Technology [Internet]. 2022 Apr 15 [cited 2024 Sept 20]; Available from: https://journals.sagepub.com/doi/full/10.1155/2022/5820207
Kumar P, Chauhan MS. Adsorption of chromium (VI) from the synthetic aqueous solution using chemically modified dried water hyacinth roots. Journal of Environmental Chemical Engineering. 2019 Aug;7(4):103218.
Blanes PS, Bordoni ME, González JC, García SI, Atria AM, Sala LF, et al. Application of soy hull biomass in removal of Cr(VI) from contaminated waters. Kinetic, thermodynamic and continuous sorption studies. Journal of Environmental Chemical Engineering. 2016 Mar 1;4(1):516-26.
Halmi MIE, Syed MA, Shamaan NA, Shukor MY. Mathematical Modeling of Molybdenum Reduction to Molybdenum Blue by Burkholderia sp. Strain Dr.Y27 and Model Selection Using the MOORA Method. Journal of Environmental Bioremediation and Toxicology. 2024 Dec 26;7(2):17-24.
Efron B. Bootstrap Methods: Another Look at the Jackknife. Ann Statist. 1979 Jan;7(1):1-26.
Lambert RJW, Mytilinaios I, Maitland L, Brown AM. Monte Carlo simulation of parameter confidence intervals for non-linear regression analysis of biological data using Microsoft Excel. Computer Methods and Programs in Biomedicine. 2012 Aug 1;107(2):155-63.
Langmuir I. The constitution and fundamental properties of solids and liquids. Part I. Solids. Journal of the American Chemical Society. 1916;38(11):2221-95.
Foo KY, Hameed BH. Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal. 2010;156(1):2-10.
Karnib M, Kabbani A, Holail H, Olama Z. Heavy Metals Removal Using Activated Carbon, Silica and Silica Activated Carbon Composite. Energy Procedia. 2014 Dec 31;50:113-20.
Hyder AHMG, Begum SA, Egiebor NO. Adsorption isotherm and kinetic studies of hexavalent chromium removal from aqueous solution onto bone char. Journal of Environmental Chemical Engineering. 2015 June 1;3(2):1329-36.
Divband Hafshejani L, Mortazavi P, Sabz ALiPour S, Brooman Nasab S. Isotherm and Kinetics Study of The Adsorption of Chromium (VI) From Aqueous Solution by Zizyphus Spina-christi Leaves Ash Nanoparticles. Irrigation Sciences and Engineering. 2016 Dec 21;39(4):97-110.
Taha AA, Shreadah MA, Ahmed AM, Heiba HF. Multi-component adsorption of Pb(II), Cd(II), and Ni(II) onto Egyptian Na-activated bentonite; Equilibrium, kinetics, thermodynamics, and application for seawater desalination. Journal of Environmental Chemical Engineering. 2016;4(1):1166-80.
Nag S, Mondal A, Bar N, Das SK. Biosorption of chromium (VI) from aqueous solutions and ANN modelling. Environ Sci Pollut Res. 2017 Aug 1;24(23):18817-35.
Srivastava S, Agrawal SB, Mondal MK. Synthesis, characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(VI) adsorption from aqueous solution. J Environ Sci (China). 2017 May;55:283-93.
Ahsan MdA, Jabbari V, Islam MdT, Kim H, Hernandez-Viezcas JA, Lin Y, et al. Green synthesis of a highly efficient biosorbent for organic, pharmaceutical, and heavy metal pollutants removal: Engineering surface chemistry of polymeric biomass of spent coffee waste. Journal of Water Process Engineering. 2018 Oct 1;25:309-19.
Boeykens SP, Saralegui A, Caracciolo N, Piol MN. Agroindustrial waste for lead and chromium biosorption. Journal of Sustainable Development of Energy, Water and Environment Systems. 2018;6(2):341-50.
Mahmood-Ul-Hassan M, Suthar V, Ahmad R, Yousra M. Biosorption of metal ions on lignocellulosic materials: batch and continuous-flow process studies. Environmental Monitoring and Assessment. 2018;190(5).
Mortazavian S, An H, Chun D, Moon J. Activated carbon impregnated by zero-valent iron nanoparticles (AC/nZVI) optimized for simultaneous adsorption and reduction of aqueous hexavalent chromium: Material characterizations and kinetic studies. Chemical Engineering Journal. 2018 July 1;353.
Sadiq A, Choubey A, Bajpai AK, Sadiq A, Choubey A, Bajpai AK. Biosorption of chromium ions by calcium alginate nanoparticles. Journal of the Chilean Chemical Society. 2018;63(3):4077-81.
Abilio TE, Soares BC, José JC, Milani PA, Labuto G, Carrilho ENVM. Hexavalent chromium removal from water: adsorption properties of in natura and magnetic nanomodified sugarcane bagasse. Environmental Science and Pollution Research. 2021;28(19):24816-29.
Dan-Iya BI, Shukor MY. Isothermal Modelling of the Adsorption of Chromium onto Calcium Alginate Nanoparticles. Journal of Environmental Microbiology and Toxicology. 2021 Dec 31;9(2):1-7.
Mahmoud ME, El-Said GF, Ibrahim GAA, Elnashar AAS. Effective removal of hexavalent chromium from water by sustainable nano-scaled waste avocado seeds: adsorption isotherm, thermodynamics, kinetics, and error function. Biomass Conversion and Biorefinery [Internet]. 2022; Available from: https://www.scopus.com/inward/record.uri?eid=2-s2.0-85144861871&doi=10.1007%2fs13399-022-03619-2&partnerID=40&md5=92f885dfde215c605d5baa0cebf9b79c
Freundlich H. Über die adsorption in lösungen (Over the adsorption in solution). Zeitschrift für Physikalische Chemie. 1907;57(1):385-470.
Rushton G, Karns C, Shimizu K. A critical examination of the use of the Freundlich isotherm in characterizing molecularly imprinted polymers (MIPs). Analytica Chimica Acta. 2005 Jan 3;528:107-13.
Ahmed S, Guo Y, Li D, Tang P, Feng Y. Superb removal capacity of hierarchically porous magnesium oxide for phosphate and methyl orange. Environ Sci Pollut Res. 2018 Sept 1;25(25):24907-16.
Downloads
Published
Issue
Section
License
Copyright (c) 2024 Aisha Grema, Nur Adeela Yasid, Mohd Ezuan Khayat, Mohd Badrin Hanizam Abdul Rahim, Ain Aqilah Basirun, Mohd Yunus Shukor
This work is licensed under a Creative Commons Attribution 4.0 International License.
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0) that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgement of its initial publication in this journal.
- Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access).
