• Economic and Environmental Geology
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• v.50 no.6
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• pp.545-554
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• 2017

Birnessite is one of the dominant Mn (oxyhydr)oxide phases commonly found in soil and deep ocean environments. It typically occurs as nano-sized and poorly crystalline aggregates in the natural environment. It is well known that birnessite participates in a wide variety of bio/geochemical reactions as a reactive mineral phase with structural defects, cation vacancies, and mixed valences of structural Mn. These various bio/geochemical reactions control not only the fate and transport of inorganic and organic substances in the environment, but also the formation of diverse Mn (oxyhydr)oxides through birnessite transformation. This review assessed and discussed about the phase transformation of birnessite under a wide range of environmental conditions and about the potential geochemical factors controlling the corresponding reactions in the literature. Birnessite transformation to other types of Mn (oxyhydr)oxides were affected by dissolved Mn(II), dissolved oxygen, solution pH, and co-existing cation (i.e., $Mg^{2+}$). However, there still have been many issues to be unraveled on the complex bio/geochemical processes involved in the phase transformation of birnessite. Future work on the detail mechanisms of birnessite transformation should be further investigated.

• 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.37 no.2
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• pp.73-80
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• 2015

An investigation on the removals of tetracycline (TTC), which is a family of antibiotics widely founded in the environment, from the aqueous solution by birnessite(${\delta}-MnO_2$)-mediated oxidative transformation was described. This study also examined the potential effect of the naturally occurring substances, humic acid (HA) on the oxidative transformation. The experiment was carried out in various conditions (reaction time, Mn oxide loadings, pH) and in the presence of HA as a batch test. The removals of TTC followed pseudo-first order reactions, and rate constants (k, $hr^{-1}$) for the removals of TTC were constantly increased with decreasing pH from 0.98 (pH 9) to 2.97 (pH 3). The rate constants also increased about 1.3 times when the birnessite loading increased from 1 to 2 g/L. Presence of HA (5 mg-C/L, at $pH{\geq}6$) caused some enhancement in the removals of TTC as compared to the control, and also showed the removal efficiencies of TTC in the birnessite mediated systems (TTC=0.25 mM, ${\delta}-MnO_2=2.0g/L$, pH 6) increased with increasing HA concentrations (1~10 mg-C/L). The results obtained from the oxidative transformation of TTC and the effect of HA were discussed in terms of reaction characteristics and mechanism.