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Sorption equilibrium prediction of competitive adsorption of herbicides 2,4-D and MCPA from aqueous solution on activated carbon using ANN

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Abstract

The simultaneous adsorption of two herbicides—2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA)—from their aqueous binary mixtures onto granular activated carbon was studied. The quantities adsorbed were determined by HPLC with UV detection. The experimental data were analysed using the Freundlich adsorption isotherm. The high correlation coefficients indicated that the adsorption equilibrium fitted the Freundlich isotherm well. A multilayer perceptron (MLP) (an artificial neural network model—ANN) was applied to describe the adsorption equilibrium in multicomponent systems. This enabled sorption isotherms to be predicted for all possible combinations of the two herbicides. The experimental results and the calculated data obtained from MLP for the solutions of the individual components and their mixtures suggest that MCPA is better adsorbed onto activated carbon than 2,4-D.

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Abbreviations

ANN:

Artificial neural network

b1, b2, b3, b4 :

Biases—the signals shifting according to Fig. 1 (dimensionless)

C0 :

The initial concentration of the adsorbate in solution (mmol/dm3)

Ce :

The equilibrium concentration of the adsorbate in solution (mmol/dm3)

D:

2,4-D; 2,4-dichlorophenoxyacetic acid

GAC:

Granular activated carbon

KF :

Freundlich constant indicative of the relative adsorption capacity of the adsorbent (mmol/g)·(dm3/mmol)1/n

m:

The mass of the adsorbent (g)

M:

MCPA; 4-chloro-2-methylphenoxyacetic acid

MLP:

Multilayer perceptron

n:

Freundlich constant indicative of the intensity of the adsorption (dimensionless)

N:

The number of calculated coefficients in MLP network (dimensionless)

P:

The number of experimental data, (dimensionless)

qe :

The amount of solute adsorbed per unit mass of adsorbent at equilibrium (mmol/g)

r2 :

Squared coefficient of determination (dimensionless)

R2 :

Squared correlation coefficient (dimensionless)

SBET :

Brunauer–Emmett–Teller surface area (m2/g)

Sme :

Mesopore surface area (m2/g)

V:

The volume of the solution (dm3)

Vme :

Mesopore volume (cm3/g)

Vmi :

Micropore volume (cm3/g)

wkj :

Weights of signal between neuron k and j according to Fig. 1 (dimensionless)

References

  • Abramovic, B.F., Sojic, D.V., Anderluh, V.B., Abazovic, N.D., Comor, M.I.: Nitrogen-doped TiO2 suspensions in photocatalytic degradation of mecoprop and (4-chloro-2-methylphenoxy)acetic acid herbicides using various light sources. Desalination 244, 293–302 (2009)

    Article  CAS  Google Scholar 

  • Aksu, Z., Kabasakal, E.: Batch adsorption of 2,4-dichlorophenoxy-acetic acid (2,4-D) from aqueous solution by granular activated carbon. Sep. Purif. Technol. 35, 223–240 (2004)

    Article  CAS  Google Scholar 

  • Benitez, F.J., Acero, J.L., Real, F.J., Roman, S.: Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2. J. Environ. Sci. Health B 39, 393–409 (2004)

    Article  Google Scholar 

  • Biniak, S., Derylo-Marczewska, A., Swiatkowski, A., Trykowski, G.: Analysis of the influence of adsorbate and adsorbent properties on adsorption of aromatics from aqueous solutions on the modified activated carbons. In: The International Conference on Carbon 2006, Aberdeen, Scotland 16-21.07.2006, Extended Abstracts, 3P134, 320 (2006)

  • Boye, B., Brillas, E., Dieng, M.M.: Electrochemical degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid in aqueous medium by peroxi-coagulation and photoperoxi-coagulation. J. Electroanal. Chem. 540, 25–34 (2003)

    Article  CAS  Google Scholar 

  • Brillas, E., Boye, B., Sires, I., Garrido, J.A., Rodriguez, R.M., Arias, C., Cabot, P.L., Comninellis, C.: Electrochemical destruction of chlorophenoxy herbicides by anodic oxidation and electro-Fenton using a boron-doped diamond electrode. Electrochim. Acta 49, 4487–4496 (2004)

    Article  CAS  Google Scholar 

  • Chingombe, P., Saha, B., Wakeman, R.J.: Effect of surface modification of an engineered activated carbon on the sorption of 2,4-dichlorophenoxy acetic acid and benazolin from water. J. Colloid Interf. Sci. 297, 434–442 (2006)

    Article  CAS  Google Scholar 

  • Crittenden, J.C., Luft, P., Hand, D.W., Oravitz, J.L., Loper, S.W., Arl, M.: Prediction of multicomponent adsorption equilibria using ideal adsorbed solution theory. Environ. Sci. Technol. 19, 1037–1043 (1985)

    Article  Google Scholar 

  • De Martino, A., Iorio, M., Xing, B., Capasso, R.: Removal of 4-chloro-2-methylphenoxyacetic acid from water by sorption on carbon nanotubes and metal oxide nanoparticles. RSC Advances 2, 5693–5700 (2012)

    Article  Google Scholar 

  • Derylo-Marczewska, A., Blachnio, M., Marczewski, A.W., Swiatkowski, A., Tarasiuk, B.: Adsorption of selected herbicides from aqueous solutions on activated carbon. J. Therm. Anal. Calorim. 101, 785–794 (2010)

    Article  CAS  Google Scholar 

  • Djebbar, K., Zertal, A., Sehili, T.: Photocatalytic degradation of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-methylphenoxyacetic acid in water by using TiO2. Environ. Technol. 27, 1192–1197 (2006)

    Article  Google Scholar 

  • Evangelista, S., Cooper, D.G., Yargeau, V.: The effect of structure and a secondary carbon source on the microbial degradation of chlorophenoxy acids. Chemosphere 79, 1084–1088 (2010)

    Article  CAS  Google Scholar 

  • Fontmorin, J.M., Huguet, S., Fourcade, F., Geneste, F., Floner, D., Amrane, A.: Electrochemical oxidation of 2,4-dichlorophenoxyacetic acid: analysis of by-products and improvement of the biodegradability. Chem. Eng. J. 195–196, 208–217 (2012)

    Article  Google Scholar 

  • Foo, K.Y., Hameed, B.H.: Detoxification of pesticide waste via activated carbon adsorption process. J. Hazard. Mater. 175, 1–11 (2010)

    Article  CAS  Google Scholar 

  • Freundlich, H.M.F.: Über die Adsorption in Lösungen. Z. Phys. Chem. 57, 385–470 (1906)

    CAS  Google Scholar 

  • Garcia-Segura, S., Cesar Almeida, L., Bocchi, N., Brillas, E.: Solar photoelectro-Fenton degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid optimized by response surface methodology. J. Hazard. Mater. 194, 109–118 (2011)

    Article  CAS  Google Scholar 

  • Gimeno, O., Plucinski, P., Kolaczkowski, S.T.: Removal of the herbicide MCPA by commercial activated carbons: equilibrium, kinetics, and reversibility. Ind. Eng. Chem. Res. 42, 1076–1086 (2003)

    Article  CAS  Google Scholar 

  • Hameed, B.H., Salman, J.M., Ahmad, A.L.: Adsorption isotherm and kinetic modeling of 2,4-D pesticide on activated carbon derived from date stones. J. Hazard. Mater. 163, 121–126 (2009)

    Article  CAS  Google Scholar 

  • Ignatowicz, K.: Selection of sorbent for removing pesticides during water treatment. J. Hazard. Mater. 169, 953–957 (2009)

    Article  CAS  Google Scholar 

  • Kim, T.-Y., Park, S.-S., Kim, S.-J., Cho, S.-Y.: Separation characteristics of some phenoxy herbicides from aqueous solution. Adsorption 14, 611–619 (2008)

    Article  CAS  Google Scholar 

  • Koopal, L.K., van Riemsdijk, W.H., de Wit, J.C.M., Benedetti, M.F.: Analytical isotherm equations for multicomponent adsorption to heterogeneous surfaces. J. Colloid Interface Sci. 166, 51–60 (1994)

    Article  CAS  Google Scholar 

  • Kusmierek, K., Sankowska, M., Swiatkowski, A.: Kinetic and equilibrium studies of simultaneous adsorption of monochlorophenols and chlorophenoxy herbicides on activated carbon. Desalin. Water Treat. 52, 178–183 (2014)

    Article  CAS  Google Scholar 

  • Legrouri, M., Lakraimi, M., Barroug, A., De Roy, A., Besse, J.P.: Removal of the herbicide 2,4-dichlorophenoxyacetate from water to zinc-aluminium-chloride layered double hydroxides. Water Res. 39, 3441–3448 (2005)

    Article  CAS  Google Scholar 

  • MacAdam, J., Parsons, S.A.: An investigation into advanced oxidation of three chlorophenoxy pesticides in surface water. Water Sci. Technol. 59, 1665–1671 (2009)

    Article  CAS  Google Scholar 

  • Njoku, V.O., Hameed, B.H.: Preparation and characterization of activated carbon from corncob by chemical activation with H3PO4 for 2,4-dichlorophenoxyacetic acid adsorption. Chem. Eng. J. 173, 391–399 (2011)

    Article  CAS  Google Scholar 

  • Ocampo-Perez, R., Abdel Daiem, M.M., Rivera-Utrilla, J., Méndez-Diaz, J.D., Sanchez-Polo, M.: Modeling adsorption rate of organic micropollutants present in landfill leachates onto granular activated carbon. J. Colloid Interface Sci. 385, 174–182 (2012)

    Article  CAS  Google Scholar 

  • Onbasili, D., Aslim, B.: Biodegradation of 2,4-dichlorophenoxy acetic acid (2,4-D) herbicide by pseudomonas spp Strains. Fresen. Environ. Bull. 20, 1438–1446 (2011)

    CAS  Google Scholar 

  • Prates Ramalho, J.P., Dordio, A.V., Palace Carvalho, A.J.: Adsorption of two phenoxyacid compounds on a clay surface: a theoretical study. Adsorption 19, 937–944 (2013)

    Article  CAS  Google Scholar 

  • Rivera-Utrilla, J., Sanchez-Polo, M., Abdel Daiem, M.M., Ocampo-Perez, R.: Role of activated carbon in the photocatalytic degradation of 2,4-dichlorophenoxyacetic acid by the UV/TiO2/activated carbon system. Appl. Catal. B 126, 100–107 (2012)

    Article  CAS  Google Scholar 

  • Salman, J.M., Hameed, B.H.: Adsorption of 2,4-dichlorophenoxyacetic acid and carbofuran pesticides onto granular activated carbon. Desalination 256, 129–135 (2010)

    Article  CAS  Google Scholar 

  • Salman, J.M., Njoku, V.O., Hameed, B.H.: Batch and fixed-bed adsorption of 2,4-dichlorophenoxyacetic acid onto oil palm frond activated carbon. Chem. Eng. J. 174, 33–40 (2011)

    Article  CAS  Google Scholar 

  • Sanchis, S., Polo, A.M., Tobajas, M., Rodriguez, J.J., Mohedano, A.F.: Degradation of chlorophenoxy herbicides by coupled Fenton and biological oxidation. Chemosphere 93, 115–122 (2013)

    Article  CAS  Google Scholar 

  • Shahryari, Z., Sharifi, A., Mohebbi, A.: Artificial neural network (ANN) approach for modeling and formulation of phenol adsorption onto activated carbon. J. Eng. Thermophys. 22, 322–336 (2013a)

    Article  CAS  Google Scholar 

  • Shahryari, Z., Ali Mohebbi, A., Soltani Goharrizi, A., Forghani, A.A.: Application of artificial neural networks for formulation and modeling of dye adsorption onto multiwalled carbon nanotubes. Res. Chem. Intermed. 39, 3595–3609 (2013b)

    Article  CAS  Google Scholar 

  • Sojic, D.V., Despotovic, V.N., Abazovic, N.D., Comor, M.I., Abramovic, B.F.: Photocatalytic degradation of selected herbicides in aqueous suspensions of doped titania under visible light irradiation. J. Hazard. Mater. 179, 49–56 (2010)

    Article  CAS  Google Scholar 

  • Stoytcheva, M.: Pesticides-Formulations, Effects, Fate. InTech, Rijeka (2011)

    Book  Google Scholar 

  • Tomczak, E., Kaminski, W.: Application of ANN to the sorption equilibrium modeling of heavy metal ions on clinoptilolite. Ecol. Chem. Eng. S 19(2), 227–237 (2012)

    CAS  Google Scholar 

  • Vergili, I., Barlas, H.: Removal of 2,4-D, MCPA and metalaxyl from water using Lewatit VP OC 1163 as sorbent. Desalination 249, 1107–1114 (2009)

    Article  CAS  Google Scholar 

  • Wu, X., Wang, S., Zhang, R., Gao, Z.: Prediction of the competitive adsorption isotherms of 2-phenylethanol and 3-phenylpropanol by artificial neural networks. J. Chromatogr. A 1332, 14–20 (2014)

    Article  CAS  Google Scholar 

  • Zertal, A., Molnar-Gabor, D., Malouki, M.A., Sehili, T., Boule, P.: Photocatalytic transformation of 4-chloro-2-methylphenoxyacetic acid (MCPA) on several kinds of TiO2. Appl. Catal. B: Environ. 49, 83–89 (2004)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Faculty of Process and Environmental Engineering, Lodz University of Technology, 90-924, Lodz, Poland

    Wladyslaw Kaminski

  2. Institute of Chemistry, Military University of Technology, 00-908, Warsaw, Poland

    Krzysztof Kusmierek & Andrzej Swiatkowski

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  1. Wladyslaw Kaminski
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  2. Krzysztof Kusmierek
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  3. Andrzej Swiatkowski
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Correspondence to Krzysztof Kusmierek.

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Kaminski, W., Kusmierek, K. & Swiatkowski, A. Sorption equilibrium prediction of competitive adsorption of herbicides 2,4-D and MCPA from aqueous solution on activated carbon using ANN. Adsorption 20, 899–904 (2014). https://doi.org/10.1007/s10450-014-9633-9

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