Selenium (Se), a vital trace element found naturally, plays a pivotal role for human being in low concentrations. Notably, within the spectrum of essential elements, Se possesses the most restricted range between the dietary deficiency (< 40 μg day-1) and the acute toxicity (> 400 μg day-1). Therefore, it is of paramount importance to maintain bioavailable Se levels within permissible limits in our drinking water sources. Among the various Se species, inorganic variants such as selenite (SeO3 2-) and selenate (SeO4 2-) are highly water-soluble, with SeO3 2- being notably more toxic than SeO4 2-. Consequently, the primary focus lies in effectively sequestering SeO3 2- from aquatic environments. Numerous methods have been investigated for SeO3 2- adsorption, including the use of metal oxides and carbon-based materials. Especially, iron oxides have garnered extensive attention due to their water stability and environmentally friendly properties. Nevertheless, their limited surface area and insufficient adsorption sites impose constraints on their efficacy as materials for SeO3 2- removal. Recently, metal–organic frameworks (MOFs), composed of metal centers bridged by organic linkers have increasingly focused as promising adsorbents for SeO3 2- removal, offering significant advantages such as large surface areas, high porosities, and structural versatility. Furthermore, there is a growing interest in defective MOFs, where intentional defects are introduced into the MOF structure. This deliberate introduction of defects aims to enhance the adsorption capacity by increasing the number of available adsorption sites. In this context, herein, we present the Fe-BTC (BTC = 1,3,5-benzenetricarboxylic acid) synthesized via a post-synthetic metal-ion metathesis (PSMM) approach, which is one of the defect engineering methods applied to metal sites. We employ the well-established MOF, HKUST-1, known for its substantial surface area, as the pristine MOF. While the pristine MOF has a crystalline phase, during the PSMM process, Fe-BTC is transformed into an amorphous phase by allowing the introduction of numerous metal defect sites. These introduced metal defect sites serve as Lewis acidic sites, enhancing the adsorption capability for selenite. Furthermore, despite its amorphous nature, Fe-BTC exhibits a substantial surface area and porosity comparable to that of the crystalline pristine MOF. Consequently, Fe-BTC, distinguished by its numerous adsorption sites and its high porosity, demonstrates a remarkable capacity for selenite adsorption.

The safe disposal of high-level radioactive waste (HLW), including the discharged spent nuclear fuel (SNF) and contaminated by-products produced from relevant chemical treatments, has become a serious pending problem for numerous countries that operate the nuclear power plants. The deep geological disposal (DGD) has thus far been considered the most proven and viable solution for isolation of the HLW and preventing any significant release of radionuclides into the biosphere. The DGD system consists of the multiple engineered and natural barrier components. Among them, the montmorillonite-based buffer and tunnel backfills are designed to perform the two major geochemical functions: 1) preventing the ingress of groundwater and any chemicals that compromise the safety of waste canister and 2) retarding the migration of released radionuclides by providing sufficient chemisorption sites. Therefore, it is essential to investigate the sorption mechanism of radionuclides onto montmorillonite and develop a thermodynamic reaction model in advance in order to accurately predict the long-term performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately; thus far, sorption of chemical species onto mineral adsorbents has been widely described based on the concept of sorption-desorption distribution coefficient (Kd), the value of which is intrinsically conditional, and active scientific efforts have been made to develop robust thermodynamic sorption models which offer the potential to improve confidence in demonstration of radionuclide migration under a wide range of geochemical conditions. The natural montmorillonites are generally classified into Na-type or Ca-type according to its exchangeable cation, and the Ca-montmorillonite containing clays are being considered as candidate materials for the engineered barriers of DGR in several countries; they generally have advantages of higher thermal conductivity and lower price than the Na-montmorillonite based clays, but their sorption capacities are still comparable. In this framework, we aimed to investigate the chemical interactions of Ca-montmorillonite with selenite [Se(IV)], which is a major oxyanionic species in terms of HLW disposal, and develop a reliable thermodynamic sorption model (TSM). The present work summarizes the characterization of Ca-montmorillonite separated from the newly adopted reference bentonite (Bentonil-WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. Further, its sorption behaviors with aqueous selenite species under aqueous conditions of S/L = 5 g/L, I = 0.01-0.1 m CaCl2, pH = 4.5-8.5, pCO2 = 10-3.5 atm, and T = 25°C were examined, and the resulting thermodynamic data are discussed as well.

Colorectal cancer is one of the most common types of cancer in men and women who consume a Western diet. We investigated the inhibitory effect of selenium (sodium selenite, Na2SeO3) and selenium nanoparticles (nano-Se) on experimental colon carcinogenesis in ICR mice. After a 1-week acclimation, 6-week-old mice received three intraperitoneal (i.p.) injections (experimental week 0-2) of azoxymethane (AOM, 10 mg/kg body weight, b.w.), followed by 2% dextran sodium sulfate (DSS)-containing drinking water for the next 1 week. The three groups (10 mice/group) were orally administered either distilled water (control), selenium (1.7 ppm), or nano-Se (1.7 ppm) daily for 8 weeks. The numbers of aberrant crypt foci (ACF), aberrant crypt (AC), and tumorous lesions were measured in colonic mucosa. Se and nano-Se treatments significantly decreased the number of ACF, AC, and tumorous lesions compared with the control. However, there was no significant difference between the selenium and nano-Se groups. The glutathione peroxidase (GSH-Px) activity in the liver and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity in serum, were high in the selenium and nano-Se groups, while thiobarbituric acid reactive substance (TBARS) level was low in both Se and nano-Se groups when compared with that in the control group. These findings indicate that selenium and nano-Se showed similar protective effects against colon carcinogenesis by inhibiting the development of ACF and tumorous lesions in mice.