• Journal of Korean Society of Environmental Engineers
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• v.32 no.6
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• pp.547-554
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• 2010

In this study, new manganese oxide (i.e., black-birnessite) particles with nanostructures were prepared and its physico-chemical properties and oxidative-transformation efficiency on 1,4-naphthoquinine(1,4-NPQ) in the presence of reactive mediator was investigated. The results were also compared with that of the manganese oxide (i.e., brown-birnessite) particles synthesized by classical McKenzie method. Analysis of XRD and SEM data show that the particles are a single phase corresponding to a birnessite-based manganese oxide with cotton ball-like shapes containing nanofibers. In batch experiments, removals of 1,4-NPQ by the black-birnessite follows pseudo-first-order kinetics and the rate constant values obtained are greater about 2.3 times than that of the brown-birnessite in spite of its lower surface area (41.0 vs 19.80 $m^2/g$). The results can be explained by the higher crystallinity and nano structured features of the back-birnessite particles, which give higher reactivity for the removals of the quinone compound. HPLC analysis of the reaction products confirmed that the balck-birnessites removed 1,4-NPQ through cross-coupling reaction in the presence of catechol as a reactive mediator.

• Korean Journal of Soil Science and Fertilizer
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• v.32 no.4
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• pp.327-332
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• 1999

Manganese (Mn) oxides in soils have been a research subject since they react with nutrients and contaminants and Mn itself is an essential element for plant growth. Birnessite was synthesized in the presence of iron (Fe) in the precipitating solution. Influence of Fe, one of common elements in soils, on crytallinity, morphology, and chemical reactivity of birnessite was examined using X-ray diffraction (XRD), electron microscope, canon exchange capacity (CEC), and chromium (Cr) oxidation capacity. With increasing Fe concentration in the precipitating solution, crystallinity and crystal size decreased. Hexagonal plates of the birnessites formed at low Fe concentration were dominant and replaced more and more by aggregate of small particles with increasing the Fe concentration. There is no significant change in CEC with changing the Fe concentration. Chromium oxidation capacity of the birnessite increased with increasing the Fe concentration. Iron in the precipitating solution poisoned crystal growth by adsorption on the surface and increased nucleation. Since Fe is a common constituent under pedogenic environment and Fe and Mn oxides often coexist in Mn oxide nodules, the birnessite with small particle, low crystallinity, and high chemical reactivity is the form which is more likely to be formed in soils. The high CEC ($140cmol_ckg^{-1}$) and oxidation capacity of birnessite indicate that birnessite can be used in environment and agriculture.

• 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.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.4
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• pp.247-256
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• 2013

In this study, alginate beads containing birnessite (Bir-AB), a highly reactive oxidative catalyst for the transformation of phenolic compounds, was prepared and its 1-naphthol (1-NP) removal efficiency was investigated in a batch test. Based on scanning electron microscopy image, it can be inferred that the alginate gel cluster acts as a bridge which bind the birnessite particles together. Kinetic experiment with Bir-AB of different mixing ratios of birnessite to alginate (Bir : AG=0.25 : 1~1 : 1 w/w) indicate that pseudo-first order kinetic constants, $k(hr^{-1})$ for the 1-NP removals increased about 1.5 times when the birnessite mixing ratio was doubled. The removals of 1-NP was found to be dependent on solution pH and the pesudo-first order rate constants were increased from 0.331 $hr^{-1}$ at pH 10 to 0.661 $hr^{-1}$ at pH 4. The analysis of total organic carbon for the reaction solutions showed that a higher removal of dissolved organic carbon was achieved with Bir-AB as compared to birnessite. HPLC chromatographic analysis of the methanol extract after reaction of 1-NP with Bir-AB suggest that the reaction products could be removed through incorporation into the aliginate beads as a bound residue. Mn ions produced from the oxidative transformation of 1-NP by birnessite were also removed by sorption to Bir-AB. The Bir-AB was recovered quantitatively by simple filtration and was reused twice without significant loss of the initial reactivity.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.4
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• pp.427-437
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• 2020

Manganese nodules, which are evaluated as potential metal resources, have been found in the Arctic Ocean as well as in the abyssal plains of the Pacific and Indian Oceans. Manganese nodules exhibit strong variations in the morphology, internal texture, chemical composition and mineralogy as they grow. The relationship between the texture and chemical elemental composition during the growth process is well documented, but the mineral composition variation during the growth process is not. Because the manganese oxide minerals in nodules are fine-grained and poorly crystalline, quantitative analysis for the mineral composition is challenging for the bulk nodule sample. This study investigated the internal texture and Mn-oxide mineral composition of manganese nodules obtained from the East Siberian Sea. Semi-quantitative analysis was attempted for three main Mn-oxide minerals constituting the manganese nodules (i.e., todorokite, buserite and birnessite) using the peak area ratio of X-ray diffraction analysis graphs. In the East Siberian Sea manganese nodules, birnessite is more abundant than buserite or todorokite, and no correlation is found between the mineral composition and the internal texture. Instead a correlation is found between the relative content of todorokite and the lamellae depth. The todorokite content tends to increase from the surface to the core of the nodules, which can be attributed to a recrystallization process or difference in the growth rate within the nodule. This study shows that semi-quantitative analysis of manganese oxide minerals using the peak area ratio is useful in the mineralogical study of manganese nodules.