• Journal of Korean Society of Water and Wastewater
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• v.27 no.2
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• pp.155-164
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• 2013

The main purpose of this research was to examine the adsorption/ion exchange characteristics of radioactive species such as cesium and strontium onto synthetic Na-birnessite (sodium-birnessite). As part of efforts to investigate the sorption behavior of cesium and strontium onto synthetic Na-birnessite, batch isotherm tests were performed under different experimental conditions. Na-birnessite was synthesized by the oxidation of $Mn^{2+}$ ions in sodium hydroxide solution. The synthetic Na-birnessite was characterized by powder x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) surface area analysis. Cesium and strontium concentrations were determined by atomic absorption spectroscopy (AAS). The removal efficiency of strontium by Na-birnessite was around 95 % which was much higher than that of cesium (~ 32 %). The results imply that strontium has a higher affinity for Na-birnessite than cesium because strontium, divalent cation leads to larger electrostatic attraction than monovalent cesium.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.3
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• pp.143-152
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• 2020

Birnessite is a layered manganese oxide mineral with ~7 Å of d-spacing. Because of its high cation exchange capacity, birnessite greatly impacts the chemical compositions of ground water and fluids in sediment pores. Understanding the cation exchange mechanisms requires atomistic investigations of the crystal structures and coordination environments of hydrated cations in the interlayer. In this study, we conducted classical molecular dynamics (MD) simulations, an atomistic simulation method of computational mineralogy, for triclinic Na-birnessite and K-birnessite whose chemical formula are from previous experiments. We report our MD simulation results of the crystal structures, coordination environments of Na⁺ and K⁺, and the polytypes of birnessite and compare them with available experimental results. The simulation results well reproduced experimental lattice parameters and provided atomic level information for the interlayer cation and water molecule sites that are difficult to distinguish in X-ray experiments. We also report that the polytype of the Mn octahedral sheets is identical between Na- and K-birnessite, but the cation positions differ from each other, demonstrating a correlation between the coordination environment of the interlayer cations and the crystal lattice parameters. This study shows that MD simulations are very promising in elucidating ion exchange reactions of birnessite.

• Analytical Science and Technology
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• v.23 no.6
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• pp.566-571
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• 2010

This paper describes the sorption behaviors of aqueous uranium ions on the K-birnessite. K-birnessite was synthesized by adding a concentrated HCl to an aqueous solution of $KMnO_4$. Physicochemical characteristics of the K-birnessite, such as structure, specific surface area and surface charge, were investigated. K-birnessite is a layered material and the $K^+$ ions exist in the interlayer of layered K-birnessite. BET specific surface area of the K-birnessite was 38.30 m2/g. The surface charge of K-birnessite was $-1.65\;C/m^2$ at pH 5.00 and ionic strength of 0.010 M $NaClO_4$, at which the sorption experiments of uranium ions were carried out. Uranium ions were incorporated into the interlayer of the K-birnessite by cation-exchange reaction with $K^+$ ions, and the distribution coefficient is quite similar to those of common ion-exchange materials. The results might be applicable in the retardation of migration of radioactive materials from the underground disposal site of high-level radioactive waste.

• 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⁺.

• 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.

• 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.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.11
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• pp.603-610
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• 2016

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

• Journal of the Korean earth science society
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• v.27 no.3
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• pp.313-327
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• 2006

This study investigated the geochernical characteristics of Mn scale formed in groundwater wells at the Damyang area. The composition of Mn scale consists mainly of MnO and $SiO_2$. The content of Mn ranges from56.61wt.% to 68.69wt.%, and $SiO_2$ content ranges from 1.56wt.% to 10.45wt.%. The contents of Mo and Ba in Mn scale increased with increased depth; whereas, the content of Zn and Pb decreased with increased depth. Birnessite, quartz and feldspars were identified in Mn scales using x-ray powder diffraction studies. The IR absorption bands for Mn scales show major absorption band due to OH stretching, adsorbed molecular water, and birnessite stretching, respectively. In the SEM and EDS analysis, the Mn scale consists of botryoidal, spherical, spherulite, and empty straw structure. Those structure may be precipitated simply due to oversaturation with concentrated Mn content or may be formed through biogenic precipitation by Lepthothrix discophora. Under microanalysis using EDS on those structure surface of Mn scales, the Mn atomic percent range from 28 to 44, and such elements revealed the presence of Si, K, Na, Ca, Cl, Cu, Zn, and Ba.

• Journal of Electrochemical Science and Technology
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• v.13 no.2
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• pp.308-320
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• 2022

The high internal resistance (R_int) that develops across the sediment microbial fuel cells (SMFC) limits their power production (~4/10 mW m^-2) that can be recovered from an initial oil-contaminated sediment (OCS). In the anolyte, R_int is related to poor biodegradation activity, quality and quantity of contaminant content in the sediment and anode material. While on the catholyte, R_int depends on the properties of the catholyte, the oxygen reduction reaction (ORR), and the cathode material. In this work, the main factors limiting the power output of the SMFC have been minimized. The power output of the SMFC was increased (47 times from its initial value, ~4 mW m^-2) minimizing the SMFC R_int (28 times from its initial value, 5000 ohms), following the main modifications. Anolyte: the initial OCS was amended with several amounts of gasoline and kerosene. The best anaerobic microbial activity of indigenous populations was better adapted (without more culture media) to 3 g of kerosene. Catholyte: ORR was catalyzed in birnessite/carbon fabric (CF)-cathode at pH 2, 0.8M Na₂SO₄. At the class level, the main microbial groups (Gammaproteobacteria, Coriobacteriia, Actinobacteria, Alphaproteobacteria) with electroactive members were found at C-anode and were associated with the high-power densities obtained. Gasoline is more difficult to biodegrade than kerosene. However, in both cases, SMFC biodegradation activity and power output are increased when ORR is performed on birnessite/CF in 0.8 M Na₂SO₄ at pH 2. The work discussed here can focus on bioremediation (in heavy OCS) or energy production in future work.

• Journal of the Mineralogical Society of Korea
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• v.3 no.1
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• pp.34-43
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• 1990

Crystal-chemical study of hexagonal 7$\AA$ phyllomanganate minerals reveals that they have hexagonal layer structures with variable c dimensions which depend on the nature of interlayer cations and content of water molecules between edge-sharing [MnO6] octahedral layers. Approximately one out of nine octahedral sites is statistically vacant, leading to the general unit cell formula R2xMn4+1-xO2.nH2O, where R=Ca, Mn2+, Mg, K, Na;x=0.09-0.14 ; n-0.37-0.84. Z=1. The minerals of this formula fall under the name of rancieite group. It includes Ca-diminant (rancieite), Mn2+-dominant (takanelite), Na-dominant (birnessite), and Mg-dominant members. Minerals of the rancieite group occur predominantly in two different hydration states, i.e., n shows the values around 0.35 and 0.75. It is suggested that minerals of higher hydration state be called as species(i.e., rancieite, etc.) and those of lower hydration state be called as dehydrated varieties(i.e., dehydrated rancieite,etc.).