Original Research PaperInvestigation of adsorption properties of oxytetracycline hydrochloride on magnetic zeolite/Fe3O4 particles
Graphical abstract
Zeolite/Fe3O4 synthesis by chemical co-precipitation method.
Introduction
Antibiotics are pharmaceutical compounds widely used in human medicine and veterinary [1]. They enter the water cycle as main compounds and metabolites due to partially metabolized [2]. In recent studies, antibiotic residues were determined in soil [3], groundwater [4], wastewater [5], tap water [6], surface water [7]. Wastewaters that emerge from industry, hospitals, aquaculture, and households are the most important sources of antibiotic pollution in aquatic environments [8]. The presence of antibiotic pollution in the environment causes potential toxic effects on microorganisms, plants, animals, and humans [9]. Tetracyclines (TCs) are one of the most widely used antibiotics in aquafarming and veterinary medicine [10]. Most studies have shown that TCs do not fully remove from wastewater treatment plants [11], [12], [13]. For the removal of TCs from wastewater, adsorption [14], membrane filtration [15], advanced osmosis [16], electrochemical method [17] and photocatalysis [18] are used. Among these methods, adsorption is the most efficient and widely used treatment method [19]. Natural zeolites are hydrated aluminosilicate minerals with large specific surface area and high cation exchange capacity (CEC) due to extended isomorphic substitution of Si4+ by Al3+ in tetrahedra [20]. Recently, zeolites have been used frequently in the adsorption process due to their ease of accessibility, specific properties, and low cost [21]. The adsorption potential of the zeolite surface can be significantly improved by using various modification methods [22]. Among these modifications, the adsorbent can be easily separated from the solution by applying an external magnetic field, with particles having a relatively high surface area, a smaller particle size, and a porous structure by magnetic modification. In particular, the excellent magnetic property of the powder allows it to be easily recovered by magnetic separation technology after adsorption or regeneration [23], [24]. Since magnetite (Fe3O4) shows high dispersion stability and magnetic susceptibility, it is widely used as a magnetic material [25]. The methods used in the preparation of magnetic composites are sol–gel [26], co-precipitation [27], thermal degradation [28], microwave method [29], hydrothermal [30], solvothermal synthesis [31] and mechanochemical process [32]. The co-precipitation method is frequently preferred for the removal of impurities in water due to its advantages such as synthesizing particles of similar size, ease of application and less chemical use. In the chemical co-precipitation method, magnetic particles are generally obtained by adding a base to the aqueous solution of Fe(II) and Fe(III) salts [33]. The chemical reaction of Fe3O4 precipitation is given by the following equation [34].Fe3+ + Fe2+ + 8OH− ↔ 2Fe(OH)3 (s) + Fe(OH)2 (s) → Fe3O4 (s) + 4H2O
Iron oxides have been used for zeolite modification in wastewater treatment. Iron compounds show high affinity for TC compounds due to surface complexation. The iron ion can increase the adsorption capacity by establishing a bond between the zeolite and TC molecule [35]. Removal of antibiotics such as cephalexin [36], ceftazidime [37], diclofenac, naproxen, gemfibrozil, ibuprofen [38] from aqueous solutions with magnetic zeolites has been successfully studied. Abadi et al. (2019) investigated TC adsorption on zeolite 13X and Fe3+ modified zeolite 13X. Adsorption data were best described with Langmuir isotherms. The maximum adsorption capacity of the modified zeolite for TC adsorption was calculated as 204 mg/g, which is approximately four times higher than the unmodified zeolite [35]. Liu et al. (2015) used modified zeolite X with zerovalent iron particles (NZVI) to remove TC from water. The adsorption capacity of the TC reached 476.2 mg/g by magnetic modification. Adsorption isotherms were well described by Langmuir isotherm model and adsorption kinetics followed both pseudo second order and intraparticle diffusion models [39]. In the present study, the adsorption of OTC-HCL on zeolite/Fe3O4 was investigated. It has been observed that zeolite/Fe3O4 can be used effectively in the removal of antibiotics from aqueous solutions.
The amount of OTC-HCL adsorbed per gram of zeolite/Fe3O4 and the adsorption efficiency were determined [40]. Adsorption of OTC-HCL on zeolite/Fe3O4 examined with Langmuir [41], Freundlich [35], Dubinin Radushkevich (D-R) [41] and Temkin [42] isotherm models. Adsorption of OTC-HCL on zeolite/Fe3O4 particles was investigated with pseudo first order, pseudo second order kinetic, intraparticle diffusion and Elovich models. Thermodynamic parameters were calculated between 298 and 323 K [43]. Experiments were performed using optimum values in Table 2.
Section snippets
Material
In this study, OTC-HCL (Fig. 1) and natural clinoptilolite were provided by Deva Holding Inc. and Gordes Zeolite Inc. which are in İstanbul and İzmir in Turkey respectively. Natural clinoptilolite was obtained from the Gördes region in Manisa, also known as western Anatolian clinoptilolite (Table 1). The chemical name of the clinoptilolite is hydrated sodium–potassium-calcium-alumino-silicate. FeSO4·7H2O and NaOH, FeCl3·6H2O, NH4OH were obtained from Merck, Boston USA Chemistry, Sigma-Aldrich,
Optimization of parameters affecting adsorption
Adsorption studies were carried out at a constant stirring speed of 250 rpm. Zeolite/Fe3O4 with a particle size of 0–600 µ was used in the experiments. The effects of pH, adsorbent dosage, contact time, initial concentration, and temperature on adsorption of OTC-HCL were investigated. The optimum parameters were determined (Fig. 2 a-f) and shown in Table 2.
VSM analysis
The magnetic properties of zeolite/Fe3O4 were analyzed using a vibrating sample magnetometer in an operational magnetic field between 0 and 15 K at room temperature. As a result of the analysis, the internal hysteresis loop of the zeolite/Fe3O4 showed an “S” shaped curve at magnetic ambient temperature (Fig. 5). Zeolite/Fe3O4 particles were superparamagnetic that revealing the smaller loop area. The saturation magnetization (Ms) of the zeolite/Fe3O4 was calculated as 4.431 emu/g with a
Conclusion
Adsorption of OTC-HCL on zeolite/Fe3O4 was examined at pH: 6 at 100 mg/L OTC-HCL for 240 min. Experiments were applied with 0–600 µ and 0.1 g zeolite/Fe3O4 at 298–323 K and a constant stirring speed of 250 rpm. Considering the correlation coefficients, the adsorption of OTC-HCL on zeolite/Fe3O4 best fitted to the Langmuir isotherm model. This showed that the adsorption of OTC-HCL on zeolite/Fe3O4 was monomolecular and the surface of the zeolite/Fe3O4 was uniform in terms of energy. Since there
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The financial support provided by the Sivas Cumhuriyet University Scientific Research Projects Unit (BAP/M-764 coded project) is gratefully acknowledged. The authors gratefully acknowledged antibiotic and zeolite provided by Deva Holding-İstanbul-Turkey and Gordes Zeolite Company-İzmir-Turkey.
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