• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• Journal of Food Hygiene and Safety
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• v.3 no.1
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• pp.7-18
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• 1988

In 1987, the level of heavy metals were determined ina total of 200 samples of 9 species of shellfish of Korea. The samples were collected at the fish. markets by 10 Public Institute of Health. The samples were whelk (Buccinum striatiBBimum), oyster (Crassostrea gigas), ark shell(Tegillarca granesa), shartnecked clam (Venerupis semidecussta), hard clam (Meretrix lusoria), top shell (Turbo cornutus), abalone (Haliotis gigantea), ark shell (Scapharea broughtonii), sea-mussel (Mytilus conuscus gould), respectively. The levels of total mercury, lead, cadmium, arsenic, copper, zinc and manganese were determined. The total mercury levels were determined by mercury analyzer using the combustion gold amalgamation method. The arsenic level were determined by spectrophotometry using colorimetric sil ver diethyldithiocarbamate method after dry ash dige8tion of the samples with magnesium oxide and magnesium nitrate. The levels of other metals were determined by inductively coupled pluma spectrophotometry after wet digestion of the samples with nitric acid and su1furic acid. The results were summerized as follows; 1. The overallranges and mean(ppm) were; Hg, ND-O.221 (0.036); Pb, 0.05-1.51 (0.37); Cd, 0.02-1.86 (0.61); As, 0.5-3.97 (1.22); Cu, 0.14-54.16 (4.93); Zn, 7.40-207.17 (30.09); Mn, 0.13-s.72 (3.40). 2. The levels of all 6 metals were found to be below the maximum permissible Iimits set by the Japan lor mercury, the Netherland for lead the Hong Kong for cadmium. The Finland for Arsenic no statutory Iimits for Zn and Mn in shellfish in any countries. 3. The results show that all the 9 species of shellfish studied, none have accumulated levels dangerous enough to pose a health problem.roblem.

• Journal of the Mineralogical Society of Korea
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• v.16 no.4
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• pp.333-339
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• 2003

A new mineral, Zn analogue of rancieite (Chimooite), has been discovered at the Dongnam mine, Korea. It occurs as compact subparallel fine­grained flaky or acicular aggregates in the massive manganese oxide ores which were formed by supergene oxidation of rhodochrosite­sulfide ores in the hydrothermal veins trending NS­N25E and cutting the Pungchon limestone of the Cambrian age. The flakes of chimooite are 0.2 mm for the largest one, but usually less than 0.05 mm. The acicular crystals are elongated parallel to and flattened on (001). This mineral shows gradation to rancieite constituting its marginal part, thus both minerals are found in one and the same flake. Color is bluish black, with dull luster and brown streak in globular or massive aggregates. Cleavage is perfect in one direction. The hardness ranges from 2.5 to 4. Under reflected light it is anisotropic and bireflectant. It shows reddish brown internal reflection. Chemical analyses of different parts of both minerals suggest that rancieite and chimooite constitute a continuous solid solution series by cationic substitution. The empirical chemical formula for chimooite has been calculated following the general formula, $R_2_{x}$ M $n^{4+}$$_{9­x}$ $O_{18}$ $.$n$H_2O$ for the 7 $\AA$ phyllomanganate minerals, where x varies from 0.81 to 1.28 in so far studied samples, thus averaging to 1.0. Therefore, the formula of Zn­rancieite is close to the well­known strochiometric formula $_Mn_4^{4+}$ $O_{9}$ $.$4$H_2O$. The mineral has the formula (Z $n_{0.78}$N $a_{0.15}$C $a_{0.08}$M $g_{0.01}$ $K_{0.01}$)(M $n^{4+}$$_{3.98}$F $e^{3+}$$_{0.02}$)$_{4.00}$ $O_{9}$ $.$3.85$H_2O$, thus the ideal formula is (Zn,Ca)M $n^{4+}$$_4$ $O_{9}$ $.$3.85$H_2O$. The mineral has a hexagonal unit ceil with a=2.840 $\AA$ c=7.486 $\AA$ and a : c = 1 : 2.636. The DTA curve shows endothermic peaks at 65, 180, 690 and 102$0^{\circ}C$. The IR absorption spectrum shows absorption bands at 445, 500, 1630 and 3400 c $m^{1}$. The mineral name Chimooite has been named in honour of late Prof, Chi Moo Son of Seoul National University.ity.versity.ity.y.

• Journal of the Mineralogical Society of Korea
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• v.21 no.4
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• pp.425-434
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• 2008

Arsenic contamination in soil and groundwater has recently been one of the most serious environmental concerns. This arsenic contamination can be originated from natural or anthropogenic sources. It has been well known that arsenic behavior in geo-environmental is controlled by various oxides or hydroxides, such as those of iron, manganese, and aluminum, and clay minerals. Among those, particularly, iron (oxy)hydroxides are the most effective scavengers for arsenic. For this reason, this study characterized arsenic adsorption of magnetite which is a kind of iron oxide in nature. The physicochemcial features of the magnetite were investigated to evaluate adsorption of arsenite [As(III)] and arsenate [As(V)] onto magnetite. In addition to experiments on adsorption equilibria, kinetic experiments were also conducted. The point of zero charge (PZC) and specific surface area of the laboratory-synthesized magnetite used as an arsenic adsorbent were measured 6.56 and $16.6\;g/m^2$, which values seem to be relatively smaller than those of the other iron (oxy)hydroxides. From the results of equilibria experiments, arsenite was much more adsorbed onto magnetite than arsenate, indicating the affinity of arsenite on magnetite is larger than arsenate. Arsenite and arsenate showed adsorption maxima at pHs 7 and 2, respectively. In particular, adsorption of arsenate decreased with increase in pH as a result of electrical repulsion caused by anionic arsenate and negatively-charged surface of magnetite. These results indicate that the surface charge of magnetite and the chemical speciation of arsenic should be considered as the most crucial factors in controlling arsenic. The results of kinetic experiments show that arsenate was adsorbed more quickly than arsenite and adsorption of arsenic was investigated to be mostly completed within the duration of 4 hours, regardless of chemical speciation of arsenic. When the results of kinetic experiments were fitted to a variety of kinetic models proposed so far, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto magnetite.

• Journal of Korean Society of Environmental Engineers
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• v.34 no.7
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• pp.445-453
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• 2012

An investigation for removal of 1-indanone (1-ID), which were commonly produced from the biological and/or chemical treatment and natural weathering of the PAHs-contaminated soils, via oxidative transformation mediated by birnessite in the presence of various phenolic mediators is described. This study also examines the potential effect of the natural occurring substance humic acid (HA) on the oxidative transformation. The experiment was carried out in aqueous phase as a batch test (10 mg/L 1-ID, 0.3 mM phenolic mediators, $1.0g/L\;{\delta}-MnO_2$, at pH 5). All of the 11 tested phenoilic mediators belong to the group of natural occurring phenols and are widely used as model constituents of humic substances. From the results of HPLC analysis, it is demonstrated that 1-ID was not reactive to birnessite itself, but it can be effectively removed in birnessite-mediated cross coupling reactions in the presence of the phenolic mediators. The percent removals of 1-ID after 2 day incubation were ranged from 9.2 to 71.2% depending on the phenolic mediators applied. The initial rate constant ($K_{int}$, $hr^{-1}$) values for the 1-ID removals obtained from the pseudo-first-order kinetic plots also widely ranged from 0.18 to 15.0. Results of the correlative analysis between the removal efficiencies and structural characteristics of phenolic mediators indicate that the transformation of the 1-ID was considerably enhanced by the addition of electron-donating substituents (e.g., -OH, $-OCH_3$) at the benzne ring, and much less enhanced by the addition of electron-withdrawing substituents (e.g., -COOH, -CHO). The presence of HA showed that removal efficiencies of 1-ID in the birnessite-phenolic mediator systems decreased with increasing HA concentrations. However at low concentration of HA (< 2 mg/L), it caused some enhancement in the removals of 1-ID as compared to the control.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.409-421
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• 2022

Achieving a highly resolved spatial distribution of Mn-bearing minerals and elements in the natural ferromanganese nodules can provide detailed knowledge of the temporal variations of geochemical conditions affecting the formation processes of nodules. While a recent study utilizing Raman spectroscopy has reported the changes in the manganate mineral phases with growth for spherical nodules from the Arctic Sea, the distributions of minerals and elements in the nodules from the shallow Arctic Sea with non-spherical forms have not yet fully elucidated. Here, we reported the micro-laser Raman spectra with varying data acquisition points along three different profiles from the center to the outermost rim of the non-spherical ferromanganese nodules collected from the East Siberian Sea (~73 m). The elemental distributions in the nodule (such as Mn, Fe, etc.) were also investigated by energy dispersive X-ray spectroscopy (EDS) analysis to observe the internal structure and mineralogical details. Based on the microscopic observation, the internal structures of a non-spherical nodule can be divided into three different regions, which are sediment-rich core, iron-rich substrate, and Mn-Fe layers. The Raman results show that the Mn-bearing mineral phases vary with the data acquisition points in the Mn-Fe layer, suggesting the changes in the geochemical conditions during nodule formation. In addition, we also observe that the mineral composition and structural characteristics depend on the profile direction from the core to the rim. Particularly, the Raman spectra obtained along one profile show the lack of Fe-(oxy)hydroxides and the noticeably high crystallinity of Mn-bearing minerals such as birnessite and todorokite. On the other hand, the spectra obtained along the other two profiles present the presence of significant amount of amorphous or poorly-ordered Fe-bearing minerals and the low crystallinity of Mn-bearing minerals. These results suggest that the diagenetic conditions varied with the different growth directions. We also observed the presence of halite in several layers in the nodule, which can be evidence of the alteration of seawater after nodule formation. The current results can provide the opportunity to obtain detailed knowledge of the formation process and geochemical environments recorded in the natural non-spherical ferromanganese nodule.

• 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.