In this work, selenium (IV) was adsorbed from aqueous solutions by the strongly basic anion exchange resin Amberlite IRA 400. Using energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM), the morphology of the resin was investigated both before and after Se(IV) sorption. In order to determine the ideal sorption conditions, a batch approach was used to examine the variables that affect the performance of Se(VI) sorption, including pH, shaking time, adsorbate dosage, starting metal ion concentrations and temperature. The sorption process was satisfactorily explained by the pseudo-second-order kinetic model, according to the experimental findings. The maximum adsorption capacity at pH 3.0 was found to be 18.52 mg/g, and the adsorption rather well followed the Langmuir adsorption isotherm. Moreover, exothermic and spontaneous sorption was the result of the thermodynamic properties (negativity of both ΔG° and ΔH°). The adsorption phase's random distribution of the resin-solution interface is indicated by the positive value of ΔSo
Research Article
Evaluation of anion exchange resin for sorption of selenium (IV) from aqueous solutions
https://doi.org/10.21203/rs.3.rs-5056450/v1
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Amberlite IRA-400 Cl−
Se(IV)
Sorption
Isotherm and Kinetics
Desorption
For the nuclear energy industry and other sectors that use radioactive materials, managing radioactive waste is a paramount challenge. Ensuring the safe and effective disposal of radioactive waste mostly involves the removal of long-lived radionuclides [1, 2]. Because it takes part in the nuclear fuel cycle and the decay of other radioactive isotopes, selenium is one such radionuclide that can be found in fission products and radioactive waste. Among the several radioactive isotopes of the element selenium that occurs naturally, selenium-79 is the most prevalent one. With a half-life of about 3.27×105 years, this isotope is a persistent and possibly dangerous part of radioactive waste [3, 4]. Selenium-79 can present long-term hazards to both human health and the environment if improperly managed. Due to its widespread application in items like semiconductors, insecticides, and photosensitive materials, selenium can leak into the environment through sources like industrial effluent and agricultural runoff [5, 6]. Because it is a necessary component for living things, it is also used in the manufacturing of ceramics, catalysts, and the medical industry [7]. Selenium (IV) has been extracted from aqueous solutions using a variety of techniques, such as solvent extraction [8], co-precipitation [9], membrane separation [10], adsorption [11], and repeated evaporation approaches [12]. One of the most promising techniques for extracting selenium is adsorption, which is regarded to be inexpensive, easy to use, and effective at eliminating Se(IV) from aqueous solutions [13]. Hematite modified magnetic nanoparticles [13], phlogopite and calcite surfaces [14], zirconium and iron oxides [15], aluminum oxide-coated sand [16], chitosan–clay composite [17], iron-coated GAC [18], nanocrystalline hydroxyapatite [19], iron oxide impregnated CNTs [20], Mg–FeCO3 [21], Fe/Si coprecipitates [22], poly(1,8-diaminonaphthalene) [23], and iron oxide nanoparticle [24] are just a few of the adsorbents that have been used to remove Se(IV) from aquatic solutions. The objective of this research was to assess the efficiency of the anion exchange resin (Amberlite IR 400) in sorption of Se(IV) from aqueous solutions. Amberlite IR 400 resin was analyzed using FT-IR, SEM, and EDX. Through the study of the isothermal, kinetic, and thermodynamic characteristics of sorption, the mechanism of sorption was further clarified.
2.1. Materials
Analytical-grade chemicals and double-distilled water were utilized to prepare all chemical solutions. BDH Chemical Company supplied Amberlite IRA 400 anion exchange resin. The key features of Amberlite IRA-400 are displayed in Table 1. Sigma-Aldrich provided the hydrochloric acid, sodium hydroxide, and selenium dioxide (SeO2).
Table 1
2.2. Characterization of the Amberlite IRA 400 resin
Before and after sorption, the characteristics of anion exchange resin (Amberlite IR 400) were examined using FT-IR, SEM, and EDX. Japan's JSM-6510 LA SEM model was used to identify the morphological properties of anion exchange resin. The resin's spectra was examined with a Nicolet IS10 Fourier transformer infrared (FT-IR) spectrometer from Meslo, USA. It was determined what elements were present in Se(VI) sorption on Amberlite IR 400 using an Oxford energy-dispersive X-ray (EDX) spectrometer (Oxford Link ISIS, Japan). The concentrations of selenium ions were determined using an atomic absorption spectrophotometer of the Model S4 Series manufactured by Thermo-electron Corporation.
2.3. Batch experimental procedures
It was studied whether Amberlite IR 400 could be used to remove Se(IV) from aquatic solutions using the batch equilibrium method. The following variables were looked at: pH, temperature, adsorbent dose, starting concentration and shaking duration. For the adsorption assays, 0.1 g of resin and 5.0 ml (100 mg/L) of Se(IV) were shaken in a shaker bath (G.F.L. 1083, Germany) at 25 oC. Selenium concentrations before and after sorption onto Amberlite IR 400 were obtained using an atomic absorption spectrophotometer. The following relationships were used to calculate the sorption capacity (qo) and sorption percent (S%) of Se(IV) absorption by Amberlite IR 400.
The initial and equilibrium concentrations of Se(IV) in the solution are shown by the symbols Co and Ce, respectively, in mg/L.V is the volume of the solution (L), and m is the weight (g) of the Amberlite IR 400 resin.
2.4. Mathematical models
A list of kinetic and isotherm models used is given in Table 2. To investigate the sorption kinetics, both pseudo-first and pseudo-second-order equations were shown. To set the experimental data, Freundlich, Langmuir, and thermodynamic models were utilized. Upon reaching equilibrium, the sorption process produces an isotherm that displays dispersion of adsorbed molecules in liquid and solid phases.
Table 2
3.1. Characterization of the resin
An energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy, and Fourier transform infrared (FTIR) spectroscopy were used to evaluate the resin's chemical and physical characteristics.
3.1.1. Fourier transformed infrared (FTIR) spectroscopy
FT-IR analysis was performed to display the structure of Amberlite (IRA 400) resin both prior to and during the sorption of Se(IV). The resulting spectrums have been recorded and presented in Fig. 1(a, b). Styrene-divinylbenzene polymeric matrix,s spectra exhibit a prominent peak at 3426 cm−1, which may be ascribed to –OH, as illustrated in Fig. 1a. The asymmetric C−H stretching vibrations of CH2 and CH3 in CH3−N are responsible for the band at 2923 cm−1 [28]. Furthermore, many peaks are seen at 1637, 1513, 1380, 1262, 1030, and 520 cm-1. These could be related to the C–X and –C–C– functional groups, as well as the C=O, S=O, and C−N stretching vibrations of benzene rings. The peaks at 1030 and 890 cm−1, respectively, are caused by the C–O and C–H bonds. Upon comparing the spectra, the FT-IR spectrum of Amberlite (IRA 400) following Se(IV) adsorption is displayed in Fig. 1b, exhibiting several discernible alterations. These modifications (at 1625, 1262, and 1024 cm-1) could therefore be the result of Se(IV) binding to adsorbent.
Figure 1
3.1.2 Scanning electron microscopy (SEM)
SEM at 50X magnification is used to examine the surface appearance of Amberlite (IR 400), as shown in Fig. 2(a, b) prior to and following the adsorption of Se(IV). It is evident that the particles in Amberlite (IR 400) have smooth, spherically-shaped surfaces. However, the surface structure following the adsorption of Se(IV) revealed a few small surface fissures rather than changes in the particle's shape, which roughly demonstrates the resin's durability.
Figure 2
3.1.3 Energy Dispersive X-ray spectroscope (EDX)
Figure 3(a, b) displays the Amberlite (IR 400) EDX spectrum both before and after the adsorption of Se(IV). Based on the EDX examination, the main components of Amberlite (IR 400) (Fig. 3a) include C (78.35%), N (7.39%), O (3.19%), and Cl (11.07%).Additionally, components C (74.29%), N (5.37%), O (3.79%), Cl (15.26%), and Se (1.29%) were detected in the Amberlite (IR 400) EDX spectrum following Se(IV) adsorption (Fig. 3b). The presence of Se elements in the loaded resin was verified by the EDX characterization.
Figure 3
3.2. Batch Sorption Studies
3.2.1. Effect of pH
Ionization characteristics of adsorbent's active sites are highly impacted by the adsorption media's pH [29]. The results of an examination into pH impact on the sorption percentage of Se(IV) from aqueous solution in the range of 1.0 to 8.0 are displayed in Fig. 4a.Upon increasing the pH from 1.0 to 3.0, it was observed that the sorption effectiveness improved from 14.92% to 80.25%. The sorption % then dropped as the pH increased.The Se(IV)speciation diagrams are displayed in Fig. 4b by the Hydra/Medusa chemical equilibrium software. Selenious acid (H2SeO3) is the main species of Se(IV) at low pH values, as this figure clearly illustrates. This explained the low values for the sorption percent at pH≤ 2. Furthermore, the dominating species biselenite (HSeO3-) emerged as the pH rose to 3.5. According to the data, the anionic resin employed in the experiment had positive charges (more H+ ions) at low pH values, which caused an electrostatic reaction to occur between the (HSeO3–) species and the resin surface's positive charge. Thus, pH 3.0 was used for the sorption process of selenium ions in the next study.
Moreover, the sorption process is accelerated at pH 3 due to the resin's chemical makeup, which includes amino functionalities in its –R3N+Cl- structure. As shown in Fig. 4c, an ion exchange reaction may be used to carry out this procedure [30, 31]. As zero-point charge verified it. At pH 3, the resin's zero-point charge (pHzpc) was determined (Fig. 4d).The sorbent surface holds positive charges at pH less than pHzpc, which increases the electrostatic attraction force with biselenite (HSeO3-). The proposed mechanism is clarified in Fig. 4c.
Figure 4
3.2.2. Effect of Shaking time
One of the most crucial factors to consider when developing a batch sorption experiment is the rate of sorption. It affects removal efficiency, contributes to contact time optimization, supports kinetics modeling, and contributes to establishing suitable experimental conditions. In each experiment, contact duration influence on selenium sorption were investigated at pH 3.0, starting concentration of 100.0 mg/L, and adsorbent mass of 10 mg. Figure 5a shows the evaluation of Se(VI) sorption as a function of shaking time, with 1.0–60.0 min, on the Amberlite IR 400 resin. Upon increasing the shaking period from 1.0 to 10.0 min, we find that the sorption percentage of Se(IV) rises from 69.62 to 82.10%. Following that, the sorption percentage held steady for 60 minutes.
The selenium adsorption process onto Amberlite IR 400 resin has been explained by two primary linear kinetic models: the pseudo-first-order model and the pseudo-second-order model (see Fig. 5b,c). Table 3 summarizes the correlation coefficient (R2) and several parameters of these kinetic models. Based on R2 = 0.999, the correlation index for pseudo-second-order is seen to be close to the unit. Furthermore, the experimental result, qe EXP = 4.11 mg/g, and the calculated qeCAL = 4.12 mg/g values match quite well. These results demonstrated that the Se(VI) adsorption on Amberlite IR 400 is adequately explained by the pseudo-second-order model.
Figure 5
Table 3
3.2.3. Effect of initial selenium ion concentration
Figure 6a illustrates how the initial concentrations of selenium affect the sorption %. With an increase in Se(VI) starting concentration from 100.0 to 200.0 mg/L, we observed a decrease in Se(VI) sorption percentage from 81.27 to 67.0%. These outcomes can be explained by the fact that, at low starting concentrations of Se(VI), there are comparatively less Se(VI) species in the solution than there are binding sites available overall on the adsorbent's surface. A high sorption efficiency results from the fact that there When more Se(VI) is introduced to the system at higher initial concentrations, the number of Se(VI) species in the solution increases but the number of binding sites remains constant. The sorption efficiency will consequently directly decline.
3.2.4. Sorption isotherm and modeling
In order to estimate Se(IV) ions interactions on adsorbent surface, adsorption isotherms at equilibrium are crucial.The experiment's outcomes were assessed using a variety of linear isotherm models.Table 4 displays the values calculated using the Se(VI) sorption slopes and intercepts obtained from Fig. 6b, c. Selenium species prefer to adsorb as a monolayer onto Amberlite IR 400 active sites, as evidenced by Langmuir model's maximum correlation coefficient of 0.999.
Figure 6
Table 4
3.2.5. Effect of adsorbent dose
Figure 7 illustrates the impact of Amberlite IRA 400 resin on Se(VI) sorption efficiency in the range of 0.10-0.20 g. After increasing adsorbent dosage from 0.10 to 0.20 g, the experiment's results showed that Se(VI)'s sorption performance increased from 81.44% to 86.62%. The higher dosage of adsorbent will result in larger active sites being accessible for selenium sorption, which is why there was a reported increase in sorption.
Figure 7
3.2.6. Effect of solution Temperature
Figure 8a shows how temperature changes between 25 and 65 °C affect the percentage of selenium that is soluble in aqueous solutions. It is demonstrated that as the temperature increases, the adsorption percentage increases gradually. It is well known that increasing the temperature increases the rate at which the sorbent molecules diffuse through the sorbent particle's interior pores and outside the boundary layer. The Ln Kd vs T-1 linear plot shown in Figure 8b's slope and intercept indicate the values of ΔHo and ΔSo, as well as the thermodynamic parameter (ΔGo), were computed. The parameters' respective values are listed in Table 5. This table shows that selenium adsorption occurs readily and spontaneously on Amberlite IRA 400 resin, as demonstrated by the negative ΔGo values. As suggested by negative ∆H° value, the adsorption process is exothermic in nature. Furthermore, positive ΔS° indicated an increase in the system's randomness.
Figure 8
Table 5
3.2.7. Desorption studies
The desorption of Se(IV) from loaded Amberlite IRA 400 resin was also performed with several desorbing agents of different concentrations. The desorbing agents used included sodium acetate, nitric acid, and hydrochloric acid. According to Table 6's data and findings, 1.0 mol/L of nitric acid, 1.0 mol/L of HCl, and 1.0 mol/L of sodium acetate were all necessary to produce a maximum Se(IV) desorping of 96.40%.
In this research, the sorption of Se(IV) was performed using (Amberlite IRA 400) resin as adsorbent under various batch adsorption experiments. To identify the Amberlite IRA 400 resin, a number of characterisation techniques were employed, including as FTIR, SEM, and EDX. The Langmuir isotherm and the pseudo-second-order kinetic model match the experimental results remarkably well. It was shown that Se(VI) has an experimental sorption capacity of 18.52 mg/g at pH 3.0. Moreover, the adsorption process was an exothermic, spontaneous reaction based on the thermodynamic properties (negativity of both ΔG° and ΔH°). In conclusion, the Amberlite IRA 400 resin exhibits great potential for selenium adsorption from aqueous solutions.
Acknowledgement
The authors thank all the staff members and colleagues of the Nuclear Fuel Technology Department, Hot Laboratories Centre of Egyptian Atomic Energy Authority for their cooperation, and useful help offered during this work.
Ethical Approval
Not applicable.
Consent to Participate.
This article does not contain any studies with human participants or animals performed by any of the authors.
Consent to Publish
Not applicable.
Authors Contributions
All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by A. El-Tantawy. Batch experiment was performend by E. M. Abuelgoud. The manuscript was written by E. M. Abuelgoud. The study was supervised by S. E. A. Sharaf El-Deen. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Funding
No funding
Competing Interests
The authors declare no competing interests.
Availability of data and materials
The data of the study can be provided by corresponding author upon reasonable request.
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Tables 1-6 are available in the Supplementary Files section.
No competing interests reported.