• Applied Biological Chemistry
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• v.37 no.5
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• pp.414-420
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• 1994

Birnessite, pyrolusite and hausmannite were synthesized and tested for the ability to oxidize Cr(III) to Cr(VI). These oxides differed in zero point of charge, surface area, and crystallinity. The kinetic study showed that Cr(III) oxidation on the Mn-oxide surface is a first-order reaction. The reaction rate was various for different oxide at different conditions. Generally the reaction by hausmannite, containing Mn(III), was faster than the others, and oxidation by pyrolusite was much slower. Solution pH and initial Cr(III) concentration had a significant effect on the reaction. Inhibited oxidation at higher pH and initial Cr(III) concentration could be due to the chance of Cr(III) precipitation or complexing on the oxide surface. Oxidations by birnessite and hausmannite were faster at lower pH, but pyrolusite exhibited increased oxidation capacity at higher pH in the range between 3.0 and 5.0. Reactions were also temperature sensitive. Although calculated activation energies for the oxidation reactions at pH 3.0 were higher than the general activation energy for diffusion, there is no experimental evidence to suggest which reaction is the rate limiting step.

• Journal of the Korean Applied Science and Technology
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• v.17 no.1
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• pp.49-53
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• 2000

For decompose carbon dioxide, manganese oxide was synthesized with $0.25M-MnSO_{4}{\cdot}nH_{2}O$ and 0.5M-NaOH by coprecipitation. We made magnetite deoxidized manganese oxide by hydrogen reduction for 1hour at $330^{\circ}C$. We investigated characteristics of catalyst, hydrogen reduction degree and decomposition rate of carbon dioxide. The structure of the hausmannite certified spinel type. The specific surface area of synthesized hausmannite and deoxidized hausmannite were $22.36m^{2}/g$, $33.56m^{2}/g$ respectively. The decomposition rate of $CO_{2}$ of deoxidized hausmannite was 57%.

• Applied Microscopy
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• v.47 no.3
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• pp.131-147
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• 2017

In this work further optical and electrical investigations of pure and Zr doped $Mn_3O_4$ (from 0 up to 20 at.%) thin films as a function of frequency. First, the refractive index, the extinction coefficient and the dielectric constants in terms of Zr content are reached from transmittance and reflectance data. The dispersion of the refractive index is discussed by means of Cauchy model and Wemple and DiDomenico single oscillator models. By exploiting these results, it was possible to estimate the plasma pulse ${\omega}_p$, the relaxation time ${\tau}$ and the dielectric constant ${\varepsilon}_{\infty}$. Second, we have performed original ac and dc conductivity studies inspired from Jonscher model and Arrhenius law. These studies helped establishing significant correlation between temperature, activation energy and Zr content. From the spectroscopy impedance analysis, we investigated the frequency relaxation phenomenon and hopping mechanisms of such thin films. Moreover, a special emphasis has been putted on the effect of the oxidation in air of hausmannite thin films to form $Mn_2O_3$ ones at $350^{\circ}C$. This intrigue phenomenon which occurred at such temperature is discussed along with this electrical study. Finally, all results have been discussed in terms of the thermal activation energies which were determined with two methods for both undoped and Zr doped $Mn_3O_4$ thin films in two temperature ranges.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.313-321
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• 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
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• v.52 no.6
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• pp.529-539
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• 2019

In this study, heavy metal removal and precipitation characteristics with pH change were studied for artificial acid mine drainage. Artificial acid mine drainage was prepared using sulfates of iron, aluminum, copper, zinc, manganese which contained in acid mine drainage from abandoned mines. The single and mixed five heavy metal samples of Fe, Al, Cu, Zn, and Mn were prepared at initial concentrations of 30 and 70 mg/L. Fe and Al were mostly removed at pH 4.0 and 5.0, respectively, and other heavy metals gradually decreased with increasing pH. Concentration changes with increasing pH show generally similar trend for single and mixed heavy metal samples. The effect of removing heavy metals from aqueous solutions is not related to the initial concentration and depends on the pH change. XRD were used for mineral identification of precipitates and crystallinity of the mineral tended to increase with increasing pH. The precipitates that produced by decreasing the concentration of heavy metals in the aqueous solution composed of Fe-goethite(FeOOH), Al-basaluminite(Al₄(SO₄)(OH)₁₀·4H₂O), Cu-connellite(Cu₁₉(OH)₃₂(SO₄)Cl₄·3H₂O) and tenorite(CuO), Zn-zincite(ZnO), and Mn-hausmannite(Mn₃O₄).

• Korean Journal of Mineralogy and Petrology
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• v.36 no.1
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• pp.33-40
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• 2023

Todorokite is a manganese oxide mineral containing Mg²⁺ in a tunnel structure in which MnO₆ octahedra share corners. In order to investigate the suitability and efficiency of high temperature-treated todorokite as a material for adsorption and fixation of Cs, Cs was ion exchanged and the amount of leached Cs from todorokite was measured. The todorokite used in this study was synthesized by transforming Na-birnessite to Mg-buserite and used as a precursor. After high temperature treatment, Cs exchanged todorokite changed to birnessite and hausmannite as the temperature increased. The amount of leached Cs was investigated for Cs exchanged todorokite which was reacted with distilled water and 1 M NaCl solution at different reaction times. In general, for the samples reacted with 1 M NaCl solution, the fixation of Cs was quite effective, although the amount of leached Cs was greater due to the ion exchange reaction with Na. As the treatment temperature increased, the amount of leached Cs increased and then decreased again, which was related to the mineral phases formed at each temperature. As birnessite was formed, the amount of leached Cs increased, but as birnessite decreased, that decreased again. As the mineral phase changed to hausemanite, the amount of Cs decreased rapidly. The results of our study show that Cs exchanged todorokite can be used as a material that effectively fixes Cs and prevents its diffusion by high temperature treatment.

• Economic and Environmental Geology
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• v.52 no.6
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• pp.509-517
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• 2019

The birnessite (7Å manganate, δ-MnO₂) which is a manganese oxide and comprises manganese nodules, is a major manganese mineral on the earth surface and a precursor in the synthesis of todorokite. In this study birnessite was synthesized by three different methods: Feng et al. (2004) and Luo et al. (1998) based on redox reaction and Ma et al. (1999) based on reduction reaction. 12 birnessite samples were synthesized by different combinations of Na⁺ and K⁺ cations based on the base (OH^-) and permanganate (MnO₄^-) reagents in the synthesis. The mineral compositions of synthesized birnessite were identified by XRD, and the two cation ratio in the mineral was measured by ICP. The products obtained after hydrothermal treatment of Mg-buserite, by the precursor of birnessite, was examined by XRD, and then phase transition to todorokite and their characteristics were compared. Our results show that the byproducts and the characteristics of phase transition by each synthetic method have different trends. Hausmannite (γ-Mn₃O₄) and feitknechtite (β-MnOOH) were formed by both methods in the redox reaction mechanism. By Feng et al. (2004)'s method, manganite (γ-MnOOH) phase only appeared when cation was predominantly Na⁺. Two birnessite samples synthesized by redox reaction mechanism showed phase transition to todorokite (10Å manganate, OMS-1) when both NaOH and KMnO₄ were used together. However, single-phase birnessite was formed by Ma et al. (1999)'s method, and phase transition was confirmed only for the sample when the cation was only composed of Na⁺.

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