Adsorption of nitrate and fluoride anions from aqueous solutions using doped magnetite-pinecone nanocomposites

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Frans, Nonhlanhla
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Vaal University of Technology
The increasing rate of pollutants, such as nitrate and fluoride from industrial and agricultural sources in the environment, especially in water bodies, is becoming alarming. Excessive nitrate and fluoride concentration in water cause environmental toxicity and hazard such as eutrophication and toxic, chronic illnesses such as methemoglobinemia. Hence, there is an urgent need to remove these pollutants from water. There have been a few successful strategies for the purification of pollutants contaminated water. Adsorption has been applied to remove pollutants from aqueous media due to its flexibility, ease of use, cost-effectiveness and ability to adsorb contaminants at low concentrations. Various adsorbents have been applied to remove nitrate and fluoride anions, and doped magnetic has shown to be effective in removing these anions. In this study, manganese doped magnetite coated pinecone (Mn-MNP-PCP) and lanthanum doped magnetite coated pinecone (La-MNP-PCP) nanocomposite were prepared using the co-precipitation method. Fourier Transform Infra-Red (FT-IR), Scanning electron microscopy (SEM), Energy-dispersive x-ray spectroscopy (EDS), Thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) were used to determine the surface groups, structure and morphology, chemical composition, thermal stability and phase determination (amorphous or crystalline) structure of the synthesised Mn-MNP-PCP and La-MNP-PCP adsorbents, respectively. In addition, batch adsorption experiments were conducted to evaluate the effects of solution pH, adsorbent dose, initial solution concentrations, contact time, adsorption kinetics, adsorption isotherm and the impact of co-existing anions on the adsorption of nitrate and fluoride ions. The mechanism of adsorption processes was also determined using equilibrium isotherm modelling results and thermodynamic parameters. The maximum adsorption capacity of Mn-MNP-PCP and La-MNP-PCP adsorbents for nitrate adsorption was 22.8 mg/g and 37.7 mg/g at solution pH 4, while the adsorption efficiency was 45.6% and 75.4%. Fluoride removal occurred at pH 2 with the adsorption capacity of 46.2 mg/g and 44.77 mg/g with the removal efficiency of 92.4 % and 89.6% on both Mn-MNP-PCP and La-MNP-PCP adsorbents. The optimum adsorbent dose for both Mn-MNP-PCP and La-MNP-PCP in the adsorption of nitrate and fluoride was 1 g/L. The optimum time for the uptake of nitrate and fluoride onto MNP-PCP and La-MNP-PCP was between 15 – 20 min. The competing phosphate and sulphate ions impacted the nitrate adsorption, while the presence of carbonate and chloride had positive nitrate adsorption onto both Mn-MNP-PCP and La-MNP-PCP nanocomposites. The decrease in nitrate adsorption may be attributed to the lower affinity of Mn-MNP-PCP and La-MNP-PCP for nitrate and a competition between the nitrate ions and co-existing anions for the active sites. The presence of all competitive ions decreased the fluoride adsorption onto Mn-MNP-PCP and La-MNP-PCP nanocomposites. The multi-valent anion with higher charge density have been reported to be more readily adsorbed than monovalent anion. The equilibrium data for nitrate and fluoride ions uptake was best described by Langmuir isotherm, which predicts the formation of ionic or covalent chemical bonds between the adsorbent and adsorbate. In the same vein, pseudo-second-order model is considerably suitable for nitrate and fluoride ions adsorption, which showed that their uptake was fast. Conclusively, La-MNP-PCP adsorbent is an effective adsorbent for nitrate adsorption, while Mn-MNP-PCP effectively trmoved fluoride ions from the aqueous solution.
M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology.
Adsorption of nitrate, Adsorption of fluoride anions, Nanocomposites, Magnetite-pinecone, Pollutant adsorption, Polluted water, Chronic illnesses, Methemoglobinemia