• Korean Journal of Mineralogy and Petrology
• /
• v.36 no.4
• /
• pp.313-321
• /
• 2023

Numerous studies have investigated the adsorptive sequestration of radioactive cesium in the natural environment. Among these studies, adsorption onto minerals and high-temperature treatment stand out as highly effective, as demonstrated by the use of zeolite. In this study, cesium was ion-exchanged with birnessite and subsequently underwent high-temperature treatment up to 1100℃ to investigate both mineral phase transformation and the leaching characteristics of cesium. Birnessite has a layered structure consisting of MnO₆ octahedrons that share edges, demonstrating excellent cation adsorption capacity. The high-temperature treatment of cesium-ion-exchanged birnessite resulted in changes in the mineral phase, progressing from cryptomelane, bixbyite, birnessite to hausmannite as the temperature increased. This differs from the phase transformation observed in the tunneled manganese oxide mineral todorokite ion-exchanged with cesium, which shows phase transformation only to birnessite and hausmannite. The leaching of cesium from cesium-ion-exchanged birnessite was estimated by varying the reaction time using both distilled water and a 1 M NaCl solution. The leaching quantity changed according to the treatment temperature, reaction time, and type of reaction solution. Specifically, the cesium leaching was higher in the sample reacted with 1 M NaCl compared to the sample with distilled water and also increased with longer reaction time. For the samples reacted with distilled water, the cesium leaching initially increased and then decreased, while in the NaCl solution, the leaching decreased, increased again, and finally nearly stopped like the sample in the distilled water for the sample treated at 1100℃. These changes in leaching are closely associated with the mineral phases formed at different temperatures. The phase transformation to cryptomelane and birnessite enhanced cesium leaching, whereas bixbyite and hausmannite hindered leaching. Notably, hausmannite, the most stable phase occurring at the highest temperature, demonstrated the greatest ability to inhibit cesium leaching. This results strongly suggest that high-temperature treatment of cesium-ion-exchanged birnessite effectively immobilizes and sequesters cesium.

• Economic and Environmental Geology
• /
• v.8 no.3
• /
• pp.117-124
• /
• 1975

Wet chemical analysis (for $MnO_2$, MnO, and $H_2O$(+)) and electron microprobe analysis (for $Fe_2O_3$ and PbO) give $MnO_2$ 74.91, MnO 11.33, $Fe_2O_3$ (total Fe) 4.19, PbO 0.03, $H_2O$ (+) 9.46, sum 99.92%. 'Available oxygen determined by oxalate titration method is allotted to $MnO_2$ from total Mn, and the remaining Mn is calculated as MnO. Traces of Ba, Ca, Mg, K, Cu, Zn, and Al were found. Li and Na were not found. The existence of (OH) is verified from the infrared absorption spectra. The analysis corresponds to the formula $Mn^{4+}{_{4.85}}(Mn^{2+}{_{0.90}}Fe^{3+}{_{0.30}})_{1.20}O_{8.09}(OH)_{5.91}$, on the basis of O=14, 'or ideally $Mn^{4+}{_{5-x}}(Mn^{2+},Fe^{3+})_{1+x}O_{8}(OH)_{6}$ ($x{\approx}0.2$). X-ray single crystal study could not be made because of the distortion of single crystals. But the x-ray powder pattern is satisfactorily indexed by an orthorhombic cell with a 9.324, b 14.05, c $7.956{\AA}$., Z=4. The indexed powder diffraction lines are 9.34(s) (100), 7.09(s) (020), 4.62(m) (200, 121), 4.17(m) (130), 3.547(s) (112), 3.212(vw) (041), 3.101(s) (300), 2.597(w) (013), 2.469(m) (331), 2.214(vw)(420), 2.098(vw) (260), 2.014 (vw) (402), 1.863(w) (500), 1.664(w) (314), 1.554(vw) (600), 1.525(m) (601), 1.405(m) (0.10.0). DTA curve shows the endothermic peaks at $250-370^{\circ}C$ and $955^{\circ}C$. The former is due to the dehydration: and oxidation forming$(Mn,\;Fe)_2O_3$(cubic, a $9.417{\AA}$), and the latter is interpreted as the formation of a hausmannite-type oxide (tetragonal, a 5.76, c $9.51{\AA}$) from $(Mn,\;Fe)_2O_3$. Infrared absorption spectral curve shows Mn-O stretching vibrations at $515cm^{-1}$ and $545cm^{-1}$, O-H bending vibration at $1025cm^{-1}$ and O-H stretching vibration at $3225cm^{-1}$. Opaque. Reflectance 13-15%. Bireflectance distinct in air and strong in oil. Reflection pleochroism changes from whitish to light grey. Between crossed nicols, color changes from yellowish brown with bluish tint to grey in air and yellowish brown to grey through bluish brown in oil. No internal reflections. Etching reactions: HCl(conc.) and $H_2SO_4+H_2O_2$-grey tarnish; $SnCl_2$(sat.)-dark color; $HNO_3$(conc.)-grey color; $H_2O_2$-tarnish with effervescence. It is black in color. Luster dull. Cleavage one direction perfect. Streak brownish black to dark brown. H. (Mohs) 2-3, very fragile. Specific gravity 3.59(obs.), 3.57(calc.). It occurs as radiating groups of flakes, flower-like aggregates, colloform bands, dendritic or arborescent masses composed of fine grains in the cementation zone of the supergene manganese oxide deposits of the Janggun mine, Bonghwa-gun, southeastern Korea. Associated minerals are calcite, nsutite, todorokite, and some undetermined manganese dioxide minerals. The name is for the mine, the first locality. The mineral and name were approved before publication by the Commission on New Minerals and Mineral Names, I.M.A.