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ISSN : 1225-0112(Print)
ISSN : 2288-4505(Online)
Applied Chemistry for Engineering Vol.33 No.4 pp.352-366
DOI : https://doi.org/10.14478/ace.2022.1073

Recent Advances in the Removal of Radioactive Wastes Containing 58Co and 90Sr from Aqueous Solutions Using Adsorption Technology

Krishnapandi Alagumalai, Jeong Hyub Ha*, Suk Soon Choi†
Department of Biological and Environmental Engineering, Semyung University, Jecheon 27236, Republic of Korea
*Department of Integrated Environmental Systems, Pyeongtaek University, Pyeongtaek 17869, Republic of Korea
Corresponding Author: Semyung University Department of Biological and Environmental Engineering, Jecheon 27236, Republic of Korea Tel: +82-43-649-1337 e-mail: sschoi@semyung.ac.kr
July 4, 2022 ; July 19, 2022 ; July 19, 2022

Abstract


Nuclear power plant operations for electricity generation, rare-earth mining, nuclear medical research, and nuclear weapons reprocessing considerably increase radioactive waste, necessitating massive efforts to eradicate radioactive waste from aquatic environments. Cobalt (58Co) and strontium (90Sr) radioactive elements have been extensively employed in energy generation, nuclear weapon testing, and the manufacture of healthcare products. The erroneous discharge of these elements as pollutants into the aquatic system, radiation emissions, and long-term disposal is extremely detrimental to humans and aquatic biota. Numerous methods for treating radioactive waste–contaminated water have emerged, among which the adsorption process has been promoted for its efficacy in eliminating radioactive waste from aquatic habitats. The current review discusses the adsorptive removal of radioactive waste from aqueous solutions using low-cost adsorbents, such as graphene oxide, metal-organic frameworks, and inorganic metal oxides, as well as their composites. The chemical modification of adsorbents to increase their removal efficiency is also discussed. Finally, the current state of 58Co and 90Sr removal performances is summarized and the efficiencies of various adsorbents are compared.



초록


    1. Introduction

    Currently, nuclear power plants and research laboratories have been industrialized rapidly because of the world population, and industry, pharmaceuticals, agriculture, and healthcare products are highly dependent on radioactive isotopes[1-3]. Radioactive elements, including 51Cr, 59Fe, 58Co, 65Zn, 54Mn, 90Sr, and 131I have been extensively employed in primary heat transport systems of nuclear reactors[4-8]. Notably, these are used as primary radiation sources in the boiling reactor during the operation, whereas neutron-activated contaminated products are deposited on the core surface. Although some effective removal processes have been developed to remove contaminants[9-12], low-level radioactive waste is frequently discharged into the environment during land-based disposal and nondestructive testing[13-15]. In addition, radioactive substances are dispersed across environmental resources via nuclear power plant explosions, leakage, and natural disasters[16-20]. In particular, 58Co and 90Sr, as the commonly produced isotopes during nuclear fission and applications requiring isotopes, are highly expelled into the environmental water sources and are presently of foremost concern[21-25]. The radionuclide 58Co is extensively employed in nuclear plants and industry; it has high radioactivity, is stable, and has a long half-life decay[26-30]. Among the various forms of cobalt by-products, 58Co and 60Co exist in the environment and appear during nuclear power generation[31-34]. Cobalt residues appear at approximately 5 mg/L in surface aquatic systems, causing harmful consequences for humans and aquatic biodiversity, as reported by the World Health Organization (WHO)[35-39]. Moreover, strontium (89Sr and 90Sr with a half-lifes of 50.4 days and 28 years, respectively) is a crucial nuclear fission by-product with high beta emission (0.546 MeV)[40-45]. The biological properties of Sr(II) are similar to those of calcium; therefore, Sr can easily replace calcium in the human body, which leads to damage of the skeletal structure and bone cancer[46,47]. The extensive discharge of nuclide wastes (90Sr and 58,60Co) in the surface and subsurface environments resulting from the Chernobyl (Ukrainian SSR, 1989) and Fukushima (Japan, 2011) nuclear accidents is well known[28,48]. These nuclides exist in various molecular forms, emit radiotoxicity, and have a long half-life. Because of the high affinity and mobility of radioactive waste, it easily accumulates in vegetation and sediments, causing long-term side effects in humans and aquatic biota[49-52]. Preventing the spread of radioactive waste, emergency treatment, safe storage of radioactive nuclides in nuclear dumps, and reducing pollution of water sources are essential challenges worldwide. Therefore, to protect organisms and the environment, these toxic radioactive wastes must be removed from wastewater.

    There are several advanced methods currently in use, such as membrane technology[53,54], coagulation-flocculation[55], chemical precipitation[56], reverse osmosis[57], advanced oxidation processes[58], ion exchange[59], photocatalysis[60], electrochemistry[61], and biological treatment[62] for the elimination of radioactive substances from wastewater before discharge into the environment. However, owing to their high cost, low feasibility, unfriendly nature, excessive energy consumption, and long processing times, these methods are rarely used[63,64]. Thus, the development of cost-effective alternative techniques is vital for solving this difficulty. Among these, adsorption is a preferred method for removing radioactive waste because of its low cost, high active surface area, availability, and high cation exchange ability[65,66].

    In this review, the technical feasibility of different inexpensive adsorbent materials, such as graphene oxide, metal-organic frameworks, and metal oxides, for radioactive waste removal from wastewater is discussed. Furthermore, chemically modified adsorbents are also discussed as a means to improve removal efficiency.

    2. Graphene oxide for removal of 58Co and 90Sr

    With rapid industrialization, vast amounts of radioactive waste have been generated, which has severe impacts on the environment and humans. Thus, efficient separation and removal of radioactive waste is vital for environmental stability and human safety. The utilization of different carbon materials for environmental remediation applications has increased significantly over the last few decades[67-70]. Yang et al. reviewed the properties and possible environmental applications of carbonaceous materials including carbon nanotubes, carbon nanofibers, fullerenes, nanodiamonds, fullerenes, and graphene. Among the various carbon nanomaterials, graphene oxide is suitable for environmental applications owing to its high-performance properties, including nontoxicity, biodegradability, high stability, flexibility, and excellent sorption capacities[71]. The graphene surface was chemically modified using different chemical methods and organic polymers to develop their active functional groups (Figure 1)[72-76]. This indicates the abundance of surface moieties, such as epoxy (-C=O), hydroxyl (-OH), and carboxyl (-COOH), making it a promising adsorbent material for the removal of pollutants from wastewater. Thus far, many studies have been successfully performed and reported on radioactive nuclides in aquatic environments[77-81].

    Lingamdinne et al. reported the synthesis of porous graphene oxide with unique physical properties using Hummer’s method[84]. The adsorption properties of the prepared GO toward Co were studied using the batch adsorption method, and the maximum adsorption capacity (Qmax) of 58Co was 21.28 mg/g. The pseudo-second-order kinetic model was used to describe the adsorption of Co onto GO. The obtained equilibrium data fit the Freundlich isotherm well. Zhao et al. used a few-layered graphene oxide nanosheets as adsorbents to remove 58Co from aqueous solutions[1]. The effects of pH and ionic strength were investigated, and the sorption of 58Co on GO was found to be strongly dependent on the acidic medium. The theoretical active surface area of GO was 2620 m2/g, and the obtained Qmax of 58Co was 68.2 mg/g at pH 6.0. As shown in Figure 2F, Wang et al. prepared different surface- modified adsorbate materials, including GO, nitrogen-doped graphene oxide, magnetic graphene oxide, and nitrogen-doped magnetic graphene oxide, to remove 58Co from wastewater[85]. The maximum sorption efficiency of GO was above 43.3 mg/g at 323 K, which fitted well with the Freundlich isotherm model. Moreover, the sorption-desorption of the cycles was investigated with 1 M NaCO3, and GO exhibited the highest reusability and chemical stability. Graphene oxide was synthesized and used for 90Sr adsorption from aqueous solutions[86]. Two possible interactions of Sr(HCOO)2 and SrCO3 were assumed between 90Sr and GO; a Qmax of 137.80 mg/g was observed at 30 °C. Furthermore, as shown in Figures 2A and B, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy indicated the involvement of oxygen- containing functional groups in 90Sr adsorption. Zhao et al. analyzed the adsorption kinetics, isotherms, and thermodynamic parameters correlating the removal of 90Sr from wastewater[87]. The adsorption of 90Sr on GO in single and binary solute systems was fitted by the Langmuir isotherm and pseudo-second-order kinetic models with high correlation coefficients (R2 = 0.995 and R2 = 0.999, respectively). Moreover, the Qmax of 90Sr on GO was 0.52 mol/g at pH 4.5 and 298 K as per the Langmuir model. Romanchuk et al. reported that the coagulation mechanism leads to the high adsorption capability of 90Sr from nuclear waste–contaminated water[8]. The Qmax of 90Sr is approximately 23.83 mg/g and the uptake adsorbent dose is 0.038 g/L (Table 1). GO is a highly effective adsorbent material for 90Sr removal and its sorption capacity and coagulation with cations make it a promising material for reliable radionuclide containment and removal. Liu et al. investigated the adsorption of 90Sr with ozonized GO nanomaterials and found an adsorption capacity of 60 mg/g[88].

    2.1. Graphene oxide-based composites for removal of 58Co and 90Sr

    The adsorption of pollutants from wastewater by GO is not very efficient because of the limited oxygen-containing functional groups that aggregate through strong interplanar interactions and coordinated pollutants with functional groups that are not very stable[89]. Thus, nitrogen- containing functional groups with different organic reagents such as ethylene diamine, amino methyl, 1-ethyl-3-(3-diethyaminopropyl) carbodiimide, N-hydroxyl succinimide, polyacrylamide, and poly-3- aminopropyltriethoxysilane oligomers have been used to modify the GO surface to improve its adsorption properties and capacity toward the effective removal of metal nuclides from environmental aquatic surfaces[90]. Alamdarlo et al. proposed the synthesis of GO surfacefunctionalized with amino methyl phosphoric acid-graphene oxide (AMPA-GO) via the Hummer’s method[91]. The Qmax values of Sr (II) with GO and AMPA-GO were 122.36 and 142.39 mg/L, respectively, at a low acidic pH of 2.0, suggesting that the functionalized GO showed excellent results when compared with GO. The experimental equilibrium data were well fitted with the pseudo-second-order and Langmuir isotherm models. A high recovery efficacy of 98% was attained in the actual samples, including estuarine water and groundwater. Qi et al. reported the synthesis of polyacrylamide reformed graphene oxide (PAM/GO) composite by grafting polyacrylamide on the GO surface to remove Sr(II) from the aqueous solution efficiently[92]. An adsorption study performed on the prepared composite exhibited a Qmax of 2.11 mmol/g at pH 8.5 and 303 K, and the adsorption capacity was comparable to that of PAM or GO alone. In addition, PAM/GO exhibited a higher absorption rate. The thermodynamic data suggest a spontaneous and endothermic process. Esterification and polymerization techniques using synthesized thiacalixarene-functionalized graphene oxide showed an adsorption capacity of 101.11 mg/L (Table 1)[93]. The absorption coefficient of the pseudo-second-order equation indicated that this model was the most suitable for describing the adsorption of 90Sr[94]. Rouby et al. analyzed the sorption of 90Sr using chitosan-reinforced GO[95]. The adsorption equilibrium data were best fitted by the Langmuir equation, and Qmax was found to be 176.6 mg/g. Huo et al. reported the sorption of 90Sr onto polyvinyl alcohol incorporated into a graphene oxide aerogel. The Qmax was calculated to be 17.48 mg/g based on experimental data[96].

    Furthermore, the surface of GO was functionalized with magnetic materials because of its high dispersion, and the poor adsorption of cations resulted in unsatisfactory performance during the adsorption process. Therefore, surface treatment is vital for GO to remove cationic radionuclides, such as 58Co and 90Sr[102]. Tayyebi et al. reported magnetic nanoparticles decorated on a GO surface (M/GO) via an ultrasonic- assisted co-precipitation method[36]. The M/GO hybrid composite removed 58Co and 90Sr from contaminated water with an absorption efficiency of 17.1 mg/L and 14.3 mg/L, respectively. Herein, the adsorption capacity of Co was two-fold higher than that of 90Sr owing to the greater affinity of 58Co toward M/GO. Liu et al. synthesized an M/GO composite using a precipitation method in the presence of GO and iron chloride[97]. The Qmax of 58Co was 12.98 mg/g on the M/GO composite. The strong adsorption observed at pH 8.5 indicates that 58Co sorption on the M/GO composite is because of inner-sphere surface complexation rather than ion exchange or outer-sphere surface complexation. The sorption isotherms of 58Co on the M/GO composite were analyzed using the Langmuir and Freundlich models, and the results from the correlation coefficient data fit the Langmuir model well. Wang et al. reported a magnetic Fe3O4/graphene oxide (Fe3O4/GO) composite which had a strong magnetic property, and catalytic sorption of 90Sr was 38.4 mg/g at pH 5.0[98]. A potential composite application of Sr(II) was performed in radioactive wastewater, and the desorption results showed excellent reusability. The adsorption of 90Sr on Fe3O4/GO was an endothermic and spontaneous process.

    Liu et al. produced inorganic metal oxide nanoparticles with graphene oxide and applied them to the removal of 58Co from aqueous solutions by batch experiments[97]. The adsorption isotherms of 58Co on M/GO and Fe3O4 were studied. Accordingly, a Qmax of 98 mg/g (58Co) was observed for the M/GO composite. Chen et al. prepared a titanate/graphene oxide composite (Figures 3G and H) via thermal treatment, which had a remarkably enhanced adsorption capacity of 58Co, above 109.8 mg/g, following the pseudo-second-order rate model[99]. The interaction mechanism of 58Co on a solid surface is shown in Figure 3I. In addition, 58Co adsorption on titanate/graphene oxide was influenced by inner-sphere surface complexation at high pH and ion exchange or outer-sphere surface complexation at low pH. Moreover, an appropriate conductive polymer and metal oxide with functional groups can increase the selectivity and adsorption capacities of GO. Zakaria et al. used a novel graphene oxide/chitosan/zirconium phosphate/silicate composite for the adsorption of radionuclides 134Cs, 60Co, 152,154Eu, and 160Tb in aqueous solution[100]. Five different kinetic models were used to fit the equilibrium data, and the adsorption process correlated well with the pseudo-second-order and particle diffusion models. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were calculated from the temperature-dependent isotherms, indicating that the adsorption was a spontaneous and endothermic process. The GO/CS/ZrP/Si composite exhibited a maximum Co(II) sorption capacity of 3.65 mg/g. Huo et al. applied a new strategy to develop the PVA/GO/MnO2 composite, and reported Qmax values of 24.02 and 28.81 mg/g for 58Co and 90Sr, respectively[101]. In the presence of other relevant co-interferences (Na+, K+, Mg2+, Ca2+, Ni2+, and Zn2+), the adsorbent exhibited higher selectivity for 58Co and 90Sr. The kinetic data for 58Co and 90Sr sorption were well fitted with the Freundlich and Langmuir models, respectively, implying that the adsorption of 58Co and 90Sr was a heterogeneous process. The synthesis of PVA/GO/MnO2 and 58Co and 90Sr removal mechanisms on the PVA/GO/MnO2 composite and scanning electron microscopy images are shown in Figure 3 (A-F).

    2.2. Interaction mechanism of radioactive waste metal ions

    Understanding the interaction mechanism between adsorbents and radioactive waste metal ions is imperative for fabricating high-efficiency materials for pollutants removal[101]. Electrostatic attraction, ion exchange, and surface complexation are all assumed to be the primary mechanisms of radioactive metal adsorption on chemically modified GO surfaces, as shown in Figure 4[102,103]. Electrostatic interactions between highly electronegative radioactive metal ions and oppositely charged GO surfaces drive adsorption[83,104]. Complexation is another likely method to adsorb radioactive metals with abundant oxygen- containing functional groups, including hydroxyl and carboxyl[82,105]. The ion-exchange reaction between radioactive divalent metal ions and protons on the oxygen-containing functional groups is an additional mechanism for improving the adsorption rate. In addition, functional groups of nitrogen- and sulfur-containing polymers covered the active sites of GO that highly attracted positive divalent metal ions, promoting a high adsorption efficiency[89,106,107].

    3. Metal-organic frameworks (MOFs) for removal of 58Co and 90Sr

    The MOF has received considerable attention from researchers owing to its remarkable physicochemical properties[108-122]. Concurrently, the material has been explored as one of the most promising materials in various fields, including for gas adsorption, catalysis, and drug delivery and separation[113-116]. Combining various metal ions and organic ligands can build numerous new structures with functional coordination groups -HH2, -X(halogen), -COOH], adjustable pore sizes, and an unsaturated metal ion center, suggesting a potential site for metal ion adsorption applications, as shown in Figure 5[117-121]. Thus, this review provides an exhaustive evaluation of recent studies on removing the toxic radioactive nuclides 58Co and 90Sr from different aqueous environments, along with the unique physicochemical properties of MOFs and modified MOFs[122-127]. The Qmax values reported to date have been in the range of 81-251 mg/g, as shown in Table 2.

    Yu et al. prepared covalent triazine frameworks (CFTs) to remove the radionuclides 58Co and 90Sr from synthetic wastewater[128]. The CFT, CFT-B, and CTF-N were investigated at different dosages; the expected removal efficiency was not attained on the CFT and CFT-B because of the overlapping of adsorption sites. Among these materials, CFT-N exhibited high removal efficiencies for 58Co and 90Sr (50.95 and 45.75 mg/g at 303 K). Yuan et al. applied a post-synthetic route to prepare a novel Schiff base containing MOFs for 58Co sorption[129]. The cobalt adsorption study was conducted at different temperatures from 288 to 318 K; the uptake capacity increased gradually, indicating that the adsorption was an endothermic process. The modified UiO-66-Schiff base showed a high sorption capacity of 256 mg/g. In addition, it displayed high selectivity in the presence of competing ions and excellent reusability using 0.01 M HCl. Figure 6A depicts the strong Sr(II) adsorption mechanism on the UiO-66-Schiff base. Furthermore, the same authors reported the removal efficiency of 58Co from wastewater using an ion-imprinted polymer (Co(II)-IIP)[130]. The maximum 58Co adsorption capacity (175 mg/g) was calculated using the Langmuir model, and the kinetic adsorption data fit well with pseudo- second-order kinetics, indicating chemisorption. Thermodynamic parameters contribute to the feasibility and spontaneity of the adsorption process. In addition, the material retained a high uptake capacity without any changes even after five adsorption-desorption cycles. Consequently, the same research group explored the 58Co adsorption capacity of three different glycine functionalized MOFs materials[131]. The MIL-101-triglycine showed high sorption (232.6 mg/g) owing to the presence of more active functional groups on its surface and a high surface area (1066 m2/g). Li et al. synthesized an environment-friendly flexible MOF membrane (MIL-101-NH2) for 58Co sorption in an aqueous solution[132]. The sorption experiments were conducted on different media of the electrolyte solution from pH 3.0 to 9.0, resulting in a Qmax of 116.3 mg/g observed at pH 8.3 and the obtained capacity was lower than that reported in the literature. Nevertheless, this is almost the highest adsorption capacity of 58Co on MIL-101-NH2 reported.

    Asgari et al. used the solvothermal technique to synthesize an MOF structure using Nd metal and benzene tricarboxylic acid[133]. The 90Sr adsorption mechanism was explained by the coordination bond between the carboxylic functional groups, and the Qmax was 58 mg/g. Analysis of N2 adsorption/desorption before and after 90Sr removal showed that the surface area of the adsorbent reduced after uptake because of the metal ions located on the internal surface and pore blocking of MOFs. Mu et al. developed the ion-trapping concept, which was used to create an efficient MOF for capturing 90Sr from nuclear waste[134]. The existence of sulfate and oxalate functional groups was confirmed in MOF-808 through Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The adsorption capacity of 90Sr on MOF- 808-SO4 (175.34 mg/g) and MOF-808-C2O4 (205.58 mg/g) showed higher efficiency than on MOF-808 (61.23 mg/g), suggesting that surface- modified sulfate/oxalate groups improved their removal efficiency. Both functionalized MOFs demonstrated excellent stability and selectivity in the presence of other co-interfering ions. Yin et al. investigated 90Sr adsorption on DtCH18C6@UiO-66-NH2[135] and obtained a Qmax value of 0.4 mg/g for 90Sr. The low adsorption retained UiO-66-NH2 than the surface-coated DutCH18C6@UiO-66-NH2 due to its lumen diameter adapting to the diameter of strontium. The adsorption of 90Sr followed the Freundlich model. Thermodynamics (ΔH°, ΔS°, and ΔG°) were retained for 90Sr sorption on DtCH18C6@ UiO-66-NH2, which was an endothermic and spontaneous process.

    Guo et al. reported on SUN-200 functionalized with 18-crown-6- ether for the adsorption of 90Sr from acidic waste[136]. The equilibrium adsorption data were fitted to the Langmuir isotherm model and the maximum sorption capacity was 44.8 mg/g. The 90Sr selectivity was examined on SNU-200 in the presence of other competing ions such as Na+, K+, Mg2+, Ca2+, and Cs+, and achieved 90% efficiency. The robust 90Sr adsorption mechanism on SNU-200 is shown in Figure 6C. Ren et al. described the introduction of dual functional groups (COOH and SO4) on the MOF (Zr-BDC-COOH-SO4), which exhibited maximum adsorption of 90Sr (67.50 mg/g) within 5 min[137]. The pseudo-second-order and Langmuir isotherm models fit well with the adsorption behavior of Zr-BDC-COOH-SO4, which demonstrates chemical and monolayer adsorption. After three cycles, it retained 70% of the adsorption capacity of the fresh sample, and rapid 90Sr adsorption on Zr-BDC-COOH-SO4 occurred via electrostatic interactions with the functional groups (Figure 6 B). Choi et al. reported the removal of 90Sr from aqueous solutions using ZnOx-MOF@MnO2, with an adsorption capacity of 147.1 mg/g[138]. The adsorption rate followed a pseudo- second-order reaction, indicating that 90Sr adsorption on ZnOx-MOF @MnO2 was controlled by chemical adsorption.

    4. Inorganic metal oxide for removal of 58Co and 90Sr

    Recently, many studies have explored efficient adsorbents and enhanced their affinities for radioactive nuclides and activated corrosion products[139-143]. Among the various adsorbents, inorganic metal oxides have received significant interest because of their versatile ion exchange properties resulting from their numerous structures with different chemical compositions[144-149]. In addition, it is considered practical and economical owing to its high radiation stability, selectivity, and excellent compatibility[150-157]. Therefore, inorganic metal adsorbents can be used to remove the radioactive pollutants in the environment.

    Sun et al. synthesized potassium niobate (KNb3O8) nanorods and sodium niobate (NaNb3O8) nanofibers under thermal conditions to adsorb radioactive 90Sr from wastewater[4]. The divalent radioactive cation 90Sr was used in the adsorption experiment on KNb3O8, and the cation exchange capacity of Nb3O8 was calculated. The divalent cation showed an adsorption capacity of 2.53 mmol/g. Similarly, NaNb3O displayed an adsorption capacity of 1.12 mmol/g. Adsorption of the toxic cation 90Sr reached 50% within 1 h. Likewise, KNb3O8 was removed rapidly within 2 h, and no changes were observed before or after adsorption on KNb3O8 owing to partial occupation by cation 90Sr on the position of K+, as shown in Figure 7 (A and B). In contrast, the XRD plane intensity decreased substantially owing to the dehydration of adsorbed 90Sr, leading to deformation in the narrow tunnel. In addition, 90Sr adsorption was confirmed by scanning electron microscopy analysis, as shown in Figure 7 (C and D). Ivanets et al. studied mesoporous manganese oxide sorbents for the sorption of radioactive strontium (85Sr), and its sorption capacity and selectivity were measured in the presence of NaCl and CaCl2[139]. The sorption capacity reached a high value of 200 mg/g with the use of H2O2 with mesoporous manganese oxide, however, a low sorption capacity of 60-80 mg/g was displayed when MnCl2 was used as the material (Table 3). The sorption capacity did not exhibit any fluctuations, and the distribution coefficient increased in the background electrolyte solution of 0.1 M NaCl. Thus, the most effective sorption and selectivity attained with H2O2 was with the use of mesoporous manganese oxide.

    Alabdullah et al. investigated the removal efficiency of three radioactive metals, Pb2+, Cs+, and Co2+, from wastewater using nano-manganese oxide (NMO)[158]. The metal ion uptake efficiency in the electrolyte buffer solution progressively increased up to pH 8.0, and low adsorption was observed at pH ˂ 2.7. The Qmax of MNO toward 58Co, calculated utilizing the Langmuir isotherm model, was 26.3 mg/g at pH 8.0. The adsorption of 58Co on NMO was assessed using a pseudo-second- order model with a high coefficient (R2=0.998). A simple method was used to prepare γ-MnO2 nanospheres with a particle size of approximately 10-18 nm and a surface area of approximately 65 m2/g[159]. Subsequently, adsorption studies were carried out at pH values ranging from 2.0 to 6.0; Qmax was observed at pH 4.0 at room temperature. With increased contact time, the adsorption of metal ions was enhanced, and the adsorption equilibrium was reached within 120 min. The Langmuir model exhibited a maximum adsorption amount of 90.1 mg/g for 58Co, and adsorption of the solute was controlled during the intra-particle diffusion process. Hassan et al. reported the use of calcium silicate-doped CuO modified with humic acid (CS-CuO-HA) for the adsorption of 58Co in an aqueous solution via a batch method[5]. Temperature is a significant parameter in the adsorption process; 58Co sorption increased as the temperature increased, suggesting an endothermic process. The sorption level of radionuclide 58Co was estimated using the Langmuir and Freundlich isotherm models, and the maximum sorption of 58Co was found to be 208.91 mg/g. The practical applicability was evaluated using a radioactive waste solution, and the removal efficiency reached up to 96.9% for CS-CuO-HA. A binary metal oxide, Fe-Mn, was designed by co-precipitation with a high Brunauer–Emmett Teller (BET) surface area of 316.76 m2/g. The Fe-Mn binary oxide exhibited a Qmax of 29.6 mg/g which was higher than that with previously reported adsorbents such as metal oxides and hydroxides under the same working conditions. Cobalt capture improved under alkaline conditions because the surface negative charge density increased; however, higher removal was achieved at pH 6.0[160]. Zhang et al. developed a manganese-antimony (MnSb) composite for the removal of 90Sr and 58Co from acidic wastewater[161]. The equilibrium adsorption isotherm data fit well with the Freundlich model, suggesting that MnSb-2 has a heterogeneous surface and non-uniform distribution of heat above the surface. In addition, the adsorption kinetics were in good agreement with pseudo-second-order kinetics, suggesting chemical sorption between the sorbent and sorbate ions. The maximum sorption of 90Sr and 58Co on MnSb-2 was 30.2 mg/L and 45.6 mg/L, respectively. Subsequently, the same authors synthesized SnSb using a sol-gel method and applied it to simultaneously capture radioactive elements 90Sr and 58Co from wastewater[162]. The BET analysis offered a large surface area of 170.8 m2/g for SnSb compared to the separate Sb2O5 (76.3 m2/g); thus, showing high sorption efficiency. The Freundlich model exhibited the maximum adsorption capacities of 24.1 mg/g and 33.3 mg/g for 90Sr and 58Co, respectively. At pH 4.0, the SnSb surface was positively charged. In addition, 90Sr and 58Co sorption occurs through steric hindrance and electrostatic interactions rather than the ion exchange of hydrated H+.

    Trinary oxides enhance the stability of an adsorbent and its removal capacity toward radiotoxicity. Attallah et al. examined the characterization and simultaneous adsorption of 134Cs and 90Sr by the nanocomposite Al2O3-ZrO2-CeO2[143]. The particle size of Al2O3-ZrO2-CeO2 was 25.13 nm, and it possessed increased hardness, high wear resistance, and good thermal stability. The maximum 90Sr sorption capacity in aqueous solution was 2.61 mg/g at pH 6.0 (Table 3). The correlation data were appropriate for a pseudo-second-order reaction, demonstrating that 90Sr adsorption on Al2O3-ZrO2-CeO2 was controlled by chemical adsorption. The selectivity of 90Sr was reduced in the presence of the possible co-interfering compounds Na(I), Mg(II), and Cr(IV). The thermodynamic parameters demonstrate the spontaneous and endothermic sorption process on Al2O3-ZrO2-CeO2.

    A combination of polyaniline with nanobentonite and manganese oxide (N-Bent-NPANI-NMn3O4) was synthesized, and different parameters were inspected and optimized during the adsorption process[157]. The removal behavior of N-Bent-NPANI-NMn3O4 showed a Qmax of 255.28 mg/g at pH 6.0 for 58Co. The highest removal capacity was observed at pH 6.0, owing to low protonation and a strong affinity for metal ions (Figure 7 H). The adsorption mechanism of 58Co was evaluated using four different isotherm models, and the results showed that the equilibrium values of the Langmuir and Freundlich models were better than those of the Temkin and D-R models. Moreover, N-Bent-NPANI-NMn3O4 exhibited a high recovery percentage (above 94.5%) in tap water and radioactive water. Kiran et al. synthesized a CTP-Fe3O4 composite by the co-precipitation method to dispose 90Sr from seawater[164]. The N2 adsorption/desorption isotherm results showed a high active surface area (473 m2/g). The microporous and macroporous forms of CTP-Fe3O4 exhibited an average pore size of 1.42 and 3.95 nm, respectively.

    5. Conclusions and future perspectives

    This review emphasizes the critical importance of reducing radioactive waste from water sources and discusses in detail the adsorptive removal of cobalt (58Co) and strontium (90Sr) nuclides from water using a variety of low-cost adsorbents, including graphene oxide, various types of MOFs, and inorganic metal oxides, using adsorption methods. In addition, adsorption has been widely used to treat aqueous solutions contaminated with radioactive wastes as it possesses several advantageous features, such as fast kinetics, wide use, easy operation, and high selectivity.

    The chemical modification of the adsorbents effectively enhanced the 58Co and 90Sr removal efficiencies. Among GO, MOF, and metal oxide-based adsorbents, MOF and metal oxide-based adsorbents show superior performance for 58Co adsorption, whereas MOF-based adsorbents show superior performance for 90Sr adsorption. Therefore, in the future, researchers should modify the surface of GO to improve its absorption efficiency.

    Also, most adsorbents can remove only a single or few radioactive nucleotides. Therefore, the development of adsorbents capable of removing a variety of radioactive nucleotides is necessary.

    However, certain limitations exist in terms of trace level contaminant removal, adsorption efficiency, stability, and reusability. Thus, researchers should concentrate their efforts on resolving these challenges and commercializing novel adsorbents in the future.

    Acknowledgement

    This work was supported by the Industrial Strategic Technology Development Program (20012763, development of petroleum residue- based porous adsorbent for industrial wastewater) funded by the Ministry of Trade, Industry, and Energy (MOTIE, Korea), and by the Green Innovative Company Growth Support Program of the Korean Ministry of Environment.

    Figures

    ACE-33-4-352_F1.gif
    (A) Different oxidation methods, (B) Abundant oxygen moieties of the GO surface, (C-D) GO surface modification with different organic polymers (Reproduced from references 82 and 83).
    ACE-33-4-352_F2.gif
    (A-B) FTIR analysis and XPS spectra for GO and GO-90Sr, (C-D) SEM image of the GO suspension before and after 90Sr adsorption, (E) EDX spectra of GO-90Sr, and (F) DOS plots of GO(-COOH)/58Co, GO(-OH)/58Co, and NGO/58Co complexes and charge density difference plot (Reproduced from references 85 and 86).
    ACE-33-4-352_F3.gif
    (A) Synthesis of PVA/GO/MnO2, (B) probable 58Co and 90Sr removal mechanism, (C-F) SEM images of 58Co and 90Sr adsorption on PVA/GO/MnO2 and PVA/GO/MnO2/58Co, 90Sr, (G-H) SEM images of TiO2 and TiO2/graphene oxide, and (I) 58Co interaction mechanism on the solid surface (Reproduced from references 99 and 101).
    ACE-33-4-352_F4.gif
    Schematic illustration of the adsorption mechanisms of radioactive metals by oxygen and nitrogen groups.
    ACE-33-4-352_F5.gif
    (A-C) Primary structure and construction of MOFs and MMOF composite, (B-D) Assemble of MOFs and surface supported carbon-based MOFs for boosting their uptake capacity (Reproduced from references 126 and 127).
    ACE-33-4-352_F6.gif
    (A) Strong 58Co adsorption mechanism on UiO-66-Schiff base, (B) Probable adsorption mechanism based on coordination interaction and electrostatic attraction with 90Sr, (C) Adsorption process of SNU-200 for 90Sr removal (Reproduced from references 121, 136, and 137).
    ACE-33-4-352_F7.gif
    (A-B) XRD patterns before and after sorption of 90Sr and Ba2+ and changes in crystal structure, (C-D) SEM images before and after adsorption of 90Sr, (E-F) SEM images of the Na-TNB membrane (G) Schematic illustration before and after ion exchange with 90Sr and Cs+ on Na-TNBs and regeneration, and (H) intercalation of nanobentonite with nano polyaniline and nano manganese oxide and adsorption of Zn(II)/Co(II) (Reproduced from references 4, 156 and 157).

    Tables

    58Co and 90Sr Adsorption Performance of Various Graphene Oxide–based Materials
    58Co and 90Sr Adsorption Performances of Various MOFbased Materials
    58Co and 90Sr Adsorption Performance of Various Metal Oxide–based Materials

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