Modification of natural zeolite clinoptilolite and ITS application in the adsorption of herbicides

Environ Technol. 2023 Nov;44(26):3949-3964. doi: 10.1080/09593330.2022.2077134. Epub 2022 May 29.

Abstract

The clinoptilolite natural zeolites (NZs) posses low herbicide adsorption capacity demanding acid-, alkali-, or salt chemical modifications that enhance its adsorption. However, this may affect the material structure and charge distribution. Alternatively, zeolites may be synthesized at a high cost and time-consuming process. Consequently, new methods, such as the hydrothermal method, for NZ modification needs to be studied. In this sense, a novel surface-modified zeolite (SMZ), using hexadecyltrimethylammonium bromide (CTAB), in acid media was produced by the hydrothermal method and applied for the adsorption of Atrazine (ATZ), Diuron (DIU) and 2,4-D. Commercial NZ and SMZ were characterized by SEM, XRD, TGA, FT-IR, AA spectroscopy, pHPZC, Zeta potential and N2-physisorption. The SMZ chosen for the adsorption experiments was the one with the highest modification yield and adsorption capacity obtained from a complete design of experiments (CTAB=0.74 ; D=12 Mesh; HCl=0.1 M; t=6 h and T=205 ºC). The adsorption experiments revealed that the SMZ adsorption capacity for the herbicide 2,4-D (qmax=9.02 mg/g) was greater than that obtained for ATZ (qmax=2.11 mg/g) and DIU (qmax=1.85 mg/g), which was explained by the presence of the hydroxyl group and by geometric characteristics of the 2,4-D. Adsorption models' fitting showed that the adsorption of 2,4-D onto SMZ were best described by pseudo-second order kinetic (k2=0.005-0.006 g/mg.min; qe,exp=7.122-8.614 mg/g) and Langmuir isothermal model (KL=0.283-0.499 L/mg; qm=7.167-7.995 mg/g). These results indicate that the hydrothermal method is a viable alternative to enable the use of NZs for the adsorption of emerging contaminants from wastewater.

Keywords: cationic surfactant; emerging contaminants; hydrothermal modification; pesticides; water treatment.

MeSH terms

  • 2,4-Dichlorophenoxyacetic Acid
  • Adsorption
  • Cetrimonium
  • Diuron
  • Herbicides*
  • Kinetics
  • Spectroscopy, Fourier Transform Infrared
  • Surface-Active Agents / chemistry
  • Zeolites* / chemistry

Substances

  • Herbicides
  • clinoptilolite
  • Zeolites
  • Cetrimonium
  • Surface-Active Agents
  • Diuron
  • 2,4-Dichlorophenoxyacetic Acid