• Journal of the Mineralogical Society of Korea
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• v.32 no.3
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• pp.151-162
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• 2019

Todorokite, a tunnel-structured manganese oxide, can contain cations within the relatively large nanopores created by the $3{\times}3$ Mn octahedra. Because todorokite is poorly crystalline and found as aggregates mixed with other phases of Mn oxides in nature, the coordination structure of cations in the nanopores is challenging to fully characterize in experiment. In the current article, we report the atomistic coordination structures of $Mg^{2+}$ ions in todorokite tunnel nanopores using the classical molecular dynamics (MD) simulations. In experiment, $Mg^{2+}$ is known to occupy the center of the nanopores. In our MD simulations, 60 % of $Mg^{2+}$ ions were located at the center of the nanopores; 40 % of the ions were found at the corners. All $Mg^{2+}$ located at the center formed the six-fold coordination with water molecules, just as the ion in bulk aqueous solution. $Mg^{2+}$ ions at the corners also formed the six-fold coordination with not only water molecules but also Mn octahedral surface oxygens. The mean squared displacements were calculated to examine the dynamic features of $Mg^{2+}$ ions in the one-dimensional (1D) nanopores. Our MD simulations indicate that the dynamic features of water molecules and the cations observed in bulk aqueous solution are lost in the 1D nanopores of todorokite.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.2
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• pp.85-92
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• 2011

Evaluation of the removal efficiencies of Fe(II) by reactive sand media coated with manganese (MCS), iron (ICS) and both of iron and manganese (IMCS) was investigated as functions of solution pH ranging from 2 to 9, reaction time and concentration of Fe(II) in a batch reactor using each reactive medium and additional oxidants such as $KMnO_4$ and NaOCl. When only Fe(II) was present in solution without any reactive medium, removal of Fe(II) was quite low below pH 5 due to a slow oxidation of Fe(II) and/or negligible precipitation but greatly increased above pH 5 due to a rapid oxidation of Fe(II) and subsequent precipitation of oxidized Fe species. ICS showed negligible efficiency on the removal of Fe(II) through adsorption. However, an efficient removal of Fe(II) was observed at low solution pH in the presence of IMCS or MCS through rapid oxidation and subsequent precipitation. Removal efficiency of Fe(II) by IMCS in the presence or absence of NaOCl was quite similar. Removal rate of Fe(II) by IMCS and additional oxidants gradually increased as the solution pH increased. From the kinetic experiments, removal pattern of Fe(II) was better described by pseudo-second-order equation than pseudo-first-order equation. A rapid removal of Fe(II) using IMCS in the presence of $KMnO_4$ was observed in the first 10 min. The initial removal rate of Fe(II) using $KMnO_4$ was 14,286 mg/kg hr. In case of using NaOCl, the removal of Fe(II) occurred rapidly in the first 6 hrs and then reached the near-equilibrium state. Removal of Fe(II) on IMCS was well expressed by Langmuir isotherm and the maximum removal capacity of Fe(II) was calculated as 1,088 mg/kg.

• Journal of the Mineralogical Society of Korea
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• v.23 no.4
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• pp.281-295
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• 2010

This paper deals with magnetic susceptibility, mineralogy, soil properties (pH, EC, CEC, loss on ignition), iron and manganese oxides, the content and partitioning of heavy metals (As, Cd, Cr, Cu, Ni, Pb, Zn), and their mutual relationship in the soil samples of an unpolluted, abandoned mine area, and industrial complex area. The various minerals derived from weathered bedrock were identified by X-ray diffraction in the unpolluted soil samples, except for the magnetic minerals. XRD analysis also revealed the existence of hematite and magnetite related to mine tailings and waste rocks in the abandoned mine area samples. The industrial complex area samples had carbonate minerals, such as calcite and dolomite, that might be due to anthropogenic deposition. The sum of the reducible, oxidizable, and residual fractions was over 80% for the abandoned mine area samples and over 50% for the industrial complex area samples using the sequential extraction method. The industrial complex area samples had a relatively high carbonate fraction that was associated with carbonate minerals. The content of aqua regia-extractable Fe, Mn, As, and Zn had a high positive correlation with the content of the dithionite-citrate-bicarbonate (DCB)-extractable method related to Fe/Mn oxide phases. The 54% and 58% of aqua regia-extractable Fe and As content, respectively, acted together with the concentrations of the DCB-extractable phases. Magnetic susceptibility values of total samples ranged from 0.005 to $2.131{\times}10^{-6}m^3kg^{-1}$. The samples including iron oxide minerals, such as hematite and magnetite, had a high magnetic susceptibility. The magnetic susceptibility showed a significant correlation with the heavy metals, Cd (r=0.544, p<0.05), Cr (r=0.714, p<0.01), Ni (r=0.645, p<0.05), Pb (r=0.703, p<0.01), and Zn (r=0.496, p<0.01), as well as Fe (r=0.608, p<0.01) and Mn (r=0.615, p<0.01). The aqua regia-extractable Fe and Mn content had a significant positive correlation with Cd, Cr, Cu, Ni, and Zn. However, the DCB-extractable Fe and Mn content had a significant positive correlation with As and Ni, indicating that the heavy metals were associated with Fe and Mn oxide minerals.

• Restorative Dentistry and Endodontics
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• v.33 no.4
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• pp.369-376
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• 2008

The aim of this study was to compare the compositions and cytotoxicity of white ProRoot MTA (white mineral trioxide aggregate) and 3 kinds of Portland cements. The elements, simple oxides and phase compositions of white MTA (WMTA), gray Portland cement (GPC), white Portland cement (WPC) and fast setting cement (FSC) were measured by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray fluorescence spectrometry (XRF) and X-ray diffractometry (XRD). Agar diffusion test was carried out to evaluate the cytotoxicity of WMTA and 3 kinds of Portland cements. The results showed that WMTA and WPC contained far less magnesium (Mg), iron (Fe), manganese (Mn), and zinc (Zn) than GPC and FSC. FSC contained far more aluminum oxide ($Al_2O_3$) than WMTA, GPC, and WPC. WMTA, GPC, WPC and FSC were composed of main phases. such as tricalcicium silicate ($3CaO{\cdot}SiO_2$), dicalcium silicate ($2CaO{\cdot}SiO_2$), tricalcium aluminate ($3CaO{\cdot}Al_2O_3$), and tetracalcium aluminoferrite ($4CaO{\cdot}Al_2O_3{\cdot}Fe_2O_3$). The significance of the differences in cellular response between WMTA, GPC, WPC and FSC was statistically analyzed by Kruskal-Wallis Exact test with Bonferroni' s correction. The result showed no statistically significant difference (p > 0.05). WMTA, GPC, WPC and FSC showed similar compositions. However there were notable differences in the content of minor elements. such as aluminum (Al), magnesium, iron, manganese, and zinc. These differences might influence the physical properties of cements.

• 한국해양학회지
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• v.27 no.3
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• pp.210-227
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• 1992

KODOS-89 area, the northwestern part of Clarion-Clarion-Clipperton fracture zones in the Northeast Pacific, was surveyed in order to study the occurrence and distribution of manganese nodules. Variations in the nodule characteristics are related mainly to seafloor topography. Nodules from abyssal plain have high Mn/Fe ratio and high Mn, Cu, Ni and Zn concentrations, whereas those from seamount are characterized by low Mn/Fe ratio and high Fe and Co concentrations. These compositional characteristics are attributed to toxic diagnosis and hydrogenesis, respectively. Nodules of the early diegenetic origin tend to accurate crystalline Mn-oxides uniformly within the topmost sediment layers and maintain a regular spheroidal, ellipsoidal to discoidal shape with rough surface textures. On the other hand, those of hydrogenetic origin are characterized by polynucleation, irregualr shape, and smooth surface textures. Nodule abundance is high (avg. 13.4 kg/m$^2$) in seamount area, resulting from ample supply of nucleating materials by auto-fragmentation of older nodules. Nodule abundance in abyssal plain is relatively low (avg. 3.9 kg/m$^2$) and tends to increase southward. This phenomenon results from facilitation of taking seed materials from adjacent seamount and enhancement of the early diagenesis by sufficient supply of organic materials. Nodule abundance is considered to be controlled primarily by seeding effects and secondly by supplies of organic materials.

• Resources Recycling
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• v.30 no.6
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• pp.43-52
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• 2021

In this study, the optimal nitration process for selective lithium leaching from powder of a spent battery cell (LiNi_xCo_yMn_zO₂, LiCoO₂) was studied using Taguchi method. The nitration process is a method of selective lithium leaching that involves converting non-lithium nitric compounds into oxides via nitric acid leaching and roasting. The influence of pretreatment temperature, nitric acid concentration, amount of nitric acid, and roasting temperature were evaluated. The signal-to-noise ratio and analysis of variance of the results were determined using L₁₆(4⁴) orthogonal arrays. The findings indicated that the roasting temperature followed by the nitric acid concentration, pretreatment temperature, and amount of nitric acid used had the greatest impact on the lithium leaching ratio. Following detailed experiments, the optimal conditions were found to be 10 h of pretreatment at 700℃ with 2 ml/g of 10 M nitric acid leaching followed by 10 h of roasting at 275℃. Under these conditions, the overall recovery of lithium exceeded 80%. X-ray diffraction (XRD) analysis of the leaching residue in deionized water after roasting of lithium nitrate and other nitrate compounds was performed. This was done to determine the cause of rapid decrease in lithium leaching rate above a roasting temperature of 400℃. The results confirmed that lithium manganese oxide was formed from lithium nitrate and manganese nitrate at these temperatures, and that it did not leach in deionized water. XRD analysis was also used to confirm the recovery of pure LiNO₃ from the solution that was leached during the nitration process. This was carried out by evaporating and concentrating the leached solution through solid-liquid separation.

• Journal of the Mineralogical Society of Korea
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• v.22 no.2
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• pp.139-151
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• 2009

Mineralogical characteristics of secondary precipitate formed at some mineral water springs in Gyeongbuk Province, Korea were studied in relation to water chemistry. The chemical water types of mineral water springs are mostly classified as $Ca-HCO_3$ type, but $Na(Ca)-HCO_3$ and $Ca-SO_4$ types are also recognized. Ca, Fe, and $HCO_3\;^-$ are the most abundant components in the water. The pH values of most springs lie in 5.76${\sim}$6.81, except Hwangsu spring having pH 2.8. Saturation indices show that all springs are supersaturated with respect to iron minerals and oxyhydroxides such as hematite and goethite. The result of particle size analysis shows that the precipitate is composed of the composite with various sizes, indicating the presence of iron minerals susceptible to a phase transition at varying water chemistry or the mixtures consisting of various mineral species. The particle size of the reddish precipitate is larger than that of the yellow brown precipitate. Based on XRD and SEM analyses, the precipitate is mostly composed of ferrihydrite (two-line type), goethite, schwertmannite, and calcite, with lesser silicates and manganese minerals. The most abundant mineral fanned at springs is ferrihydrite whose crystals are $0.1{\sim}2\;{\mu}m$ with an average of $0.5\;{\mu}m$ in size, characterized by a spherical form. It should be interestingly noted that schwertmannite forms at Hwangsu spring whose pH is very low. At Shinchon spring, Gallionella ferruginea, one of the iron bacteria, is commonly found as an indicator of the important microbial activity ascribed to the formation of iron minerals because very fine iron oxides with a spherical form are closely distributed on surfaces of the bacteria. A genetic relationship between the water chemistry and the formation of the secondary precipitate from mineral water springs was discussed.

• Journal of Environmental Impact Assessment
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• v.29 no.3
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• pp.157-181
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• 2020

Sediments from rivers, lakes and marine ports serve as end points for pollutants discharged into the water, and at the same time serve as sources of pollutants that are continuously released into the water. Until now, the contaminated sediments have been landfilled or dumped at sea. Landfilling, however, was expensive and dumping at sea was completely banned due to the London Convention. Therefore, this study applied contaminated sedimentation soil of 'Royal Palace Livestock Complex' as soil purification method. Soil remediation methods were applied to pretreatment, composting, soil washing, electrokinetics, and thermal desorption by selecting overseas application cases and domestically applicable application technologies. As a result of surveying the site for pollutant characteristics, Disolved Oxigen (DO), Suspended Solid (SS), Chemical Oxygen Demand (COD), Total Nitrogen (TN), and Total Phosphorus (TP) exceeded the discharged water quality standard, and especially SS, COD, TN, and TP exceeded the standard several tens to several hundred times. Soil showed high concentrations of copper and zinc, which promote the growth of pig feed, and cadmium exceeded 1 standard of Soil Environment Conservation Act. In the pretreatment technology, hydrocyclone was used for particle size separation, and the fine soil was separated by more than 80%. Composting was performed on organic and Total Petroleum Hydrocarbon (TPH) contaminated soils. TPH was treated within the standard of concern, and E. coli was analyzed to be high in organic matter, and the fertilizer specification was satisfied by applying the optimum composting conditions at 70℃, but the organic matter content was lower than the fertilizer specification. As a result of continuous washing test, Cd has 5 levels of residual material in fine soil. Cu and Zn were mostly composed of ion exchange properties (stage 1), carbonates (stage 2), and iron / manganese oxides (stage 3), which facilitate easy separation of contamination. As a result of applying acid dissolution and multi-stage washing step by step, hydrochloric acid, 1.0M, 1: 3, 200rpm, 60min was analyzed as the optimal washing factor. Most of the contaminated sediments were found to satisfy the Soil Environmental Conservation Act's standards. Therefore, as a result of the applicability test of this study, soil with high heavy metal contamination was used as aggregate by applying soil cleaning after pre-treatment. It was possible to verify that it was efficient to use organic and oil-contaminated soil as compost Maturity after exterminating contaminants and E. coli by applying composting.

• 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.