Anion exchange selectivity of surfactant modified clinoptilolite-rich tuff for environmental remediation

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Anion exchange selectivity of surfactant modified clinoptilolite-rich tuff for environmental remediation 

de Gennaro, B.aCatalanotti, L.aBowman, R.S.bMercurio, M.c


Journal of Colloid and Interface Science

Volume 430, 15 September 2014, Pages 178-183


a  Dipartimento di Ingegneria Chimica, Dei Materiali e della Produzione Industriale, Università di Napoli Federico II, Piazzale V. Tecchio 80, 80125 Napoli, Italy

b  New Mexico Institute of Mining and Technology, Department of Earth and Environmental Science, 801 Leroy Place, Socorro, NM 87801, United States 
c  Dipartimento di Scienze e Tecnologie, Università del Sannio, Via dei Mulini 59/A, 82100 Benevento, Italy


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Lately, the functionalization of industrial minerals with high technological properties, such as natural zeolites, is shaping as a promising approach in environmental sphere. In fact, under the specific conditions, the surface functionalization via adsorption of cationic surfactants reverses the surface charge of the mineral, enabling zeolites to simultaneously interact either with organic contaminants or inorganic anions. This aspect allows zeolites to be used in the remediation of contaminated fluids.The present research shed new light on some still not fully understood aspects concerning exchange kinetics such as anion-exchange mechanisms and selectivity of surface modified minerals. For this purpose the mineralogical characterization and the surface properties evaluation (X Ray Powder Diffraction, chemical analysis, thermal analysis, ECEC and AEC) of a clinoptilolite-rich tuff were performed, and the anion exchange isotherms of the sample, modified with hexadecyltrimethylammonium chloride or bromide (HDTMA-Cl/-Br), were determined. Ion-exchange equilibrium data of uni-uni valent reaction were obtained by solutions containing Br-, Cl-, NO3- or ClO4-. Liquid phase was analysed via high performance liquid chromatography. Thermodynamic quantities (Ka and δG0) were determined and compared with the Hofmeister series.The value of the ECEC, calculated in batch conditions, was about 137. mmol/kg, in good agreement with that evaluated in dynamic conditions, while the AEC data were different for the SMNZ-Br and -Cl samples, amounting to 137 and 106. mmol/kg, respectively, thus indicating a different compactness of the bilayer formed in the two cases. Moreover, the anion isotherm results and the mathematical evaluation of the thermodynamic parameters, demonstrated the good affinity of SMNZ-Br towards chloride, nitrate and perchlorate, and of SMNZ-Cl for nitrate and perchlorate, also endorsing the possibility of using the same thermodynamic approach developed to describe cation exchange selectivity in zeolites. Finally, it was also verified that the zeolite modified with HDTMA-Cl is able to better exploit its anion exchange capacity compared to the same zeolite modified with HDTMA-Br. © 2014 Elsevier Inc.

Author keywords

Anion exchange; Clinoptilolite; Hofmeister series; Nitrate; Perchlorate; Surfactant modified natural zeolite

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