• Economic and Environmental Geology
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• v.52 no.3
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• pp.223-230
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• 2019

The calcination of oyster shells have been studied as the possible substitute for the limestone used as an absorbent of $SO_2$ gas. However, since pure shells can not be used in calcination process, some impurities are contained and the changes in the characteristics of the calcination products are expected. In this study, the surface characteristics of the calcination products are investigated by mineralogical analysis according to the contents of NaCl, which can be derived from sea water, and sediments on the surface of the shell as impurities. The marine sediments on the shells were mainly composed of quartz, albite, calcite, small amounts of amphibole and clay minerals such as ilite, chlorite and smectite. After calcination of oyster shells mixed with 0.2-4.0 wt% sediments at $900^{\circ}C$ for 2 hours, regardless of the dehydration, dehydroxylation, and phase change of these minerals at the lower temperature than this experiment, no noticeable changes were observed on the specific surface area of the calcined product. However, when mixed with 0.1 to 2.0 wt% NaCl, the specific surface area generally increases as compared with the shell sample before calcination. The specific surface area increases with increasing amount of salt, and then decreases again. This is closely related to the changes of surface morphology. As the amount of NaCl increases, the morphology of the surface is similar to that of gel. It changes into a slightly angular, smaller particle and again looks like gel with increasing amount of NaCl. Our results show that NaCl affects morphological changes probably caused by melting of some oyster shells, but may have different effects on the specific surface area of calcination product depending on the NaCl contents.

• Economic and Environmental Geology
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• v.54 no.2
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• pp.299-308
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• 2021

Fe(II) released from mining activities is precipitated as various Fe(III)-oxyhydroxides when exposed to an oxidizing environment including mine drainage. Ferrihydrite, one of the representative precipitated Fe(III) minerals, is easy to adsorb heavy metals and other pollutants due to the large specific surface area caused by very low crystallinity. Ferrihydrite is transformed to thermodynamically more stable goethite in the natural environment. Hence, information on the transformation of ferrihydrite to goethite and the related mobility of heavy metals in the acid mine drainage is important to predict the behaviors of those elements during ferrihydrite to goethite transition. The behaviors of heavy metals during the transformation of ferrihydrite to goethite were investigated for core samples collected from an AMD treatment system in the Heungjin-Taemaek coal mine by using X-ray diffraction (XRD), chemical analysis, and statistical analysis. XRD results showed that ferrihydrite gradually transformed to goethite from the top to the bottom of the core samples. Chemical analysis showed that the relative concentration of As was significantly high in the core samples compared with that in the drainage, indicating that As was likely to be adsorbed strongly on or coprecipitated with iron oxyhydroxide. Correlation analysis also indicated that As can be easily removed from mine drainage during iron mineral precipitation due to its high affinity to Fe. The concentration ratio of As, Cd, Co, Ni, and Zn to Fe generally decreased with depth in the core samples, suggesting that mineral transformation can increase those concentrations in the drainage. In contrast, the concentration ratio of Cr to Fe increased with depth, which can be explained by the chemical bond of iron oxide and chromate, and surface charge of ferrihydrite and goethite.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.2
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• pp.95-106
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• 2021

The SO₄ in the jarosite structure can be substituted by other oxyanions, and therefore, the transition of jarosite to goethite plays a very important role in controlling the behavior of oxyanions. In this study, the phase change according to the species of the oxyanion in jarosite and the related behavior of the oxyanion was studied by mineralogical and geochemical methods when jarosite, which is coprecipitated with various oxynions, undergoes a phase change by a reductive dissolution. Jarosite substituted by five oxyanions by 5 mol% was used in this study. The mineral phase change induced by reductive dissolution using ammonium oxalate was investigated, and the order of phase transition rate of jarosite to goethite was MoO₄-jarosite ≥ SeO₄-jarosite ≥ CrO₄-jarosite > pure jarosite > SeO₃-jarosite > AsO₄-jarosite, showing that the transition rates vary depending on the substituted oxyanion. The resultant concentration of the leached Fe was slightly different depending on the type of oxyanion and time but did not show a noticeable difference. The concentration of each oxyanion leached according to the change of the mineral phase showed that the order of concentration of oxyanions was Mo > Se(SeO₃) > As > Se(SeO₄) > Cr in general, and showed a slight increase with time. This trend was related to the species of oxyanions rather than mineral phase change. The results of this study showed that the phase transition of jarosite to goethite was affected by the species of oxyanions, but this tendency did not affect the concentrations leached oxyanions.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.3
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• pp.355-365
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• 2022

Precipitation and phase transition of iron minerals in mine drainage greatly affect the behavior of trace elements. However, the precipitation of ferrihydrite, one of the major iron minerals precipitated in drainage, and the related behavior of trace elements have hardly been studied. In this study, the effects of pH change and time on mineral precipitation characteristics in mine drainage from the Munkyeong coal mine were investigated, and the behavioral changes of trace elements related to the precipitation of these minerals were studied. In the case of precipitated mineral phases, goethite was observed at pH 4, and 2-line ferrihydrite mixed with small amount of 6-line ferrihydrite was mainly identified at pH 6 or higher. In addition, it was observed that the precipitation of calcite additionally increased as the pH increased in the samples at pH 6 or higher. The occurrence of goethite was probably due to the phase change of initially precipitated ferrihydrite within a short time under the influence of low pH. Our results showed that the concentration of trace elements was strongly influenced by pH and time. With increasing time, Fe concentration in the drainage showed a abrupt decrease due to the precipitation of iron minerals, and the concentration of As existing as oxyanions in the drainage, also decreased rapidly like Fe regardless of the pH values. This decrease in As concentration was mainly due to co-precipitation with ferrihydrite, and also partly to surface adsorption on goethite at low pH in drainage. Contrary to this observation, the concentration of other trace elements, such as Cd, Co, Zn, and Ni was greatly affected by the pH regardless of the mineral species. The lower the pH value, the higher the concentration of these trace elements were observed in the drainage, and vice versa at higher pH. These results indicate that the behavior of trace elements present as cations is more greatly affected by the mineral surface charge influenced by the pH values than the type of the precipitated mineral.

• Economic and Environmental Geology
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• v.55 no.5
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• pp.531-540
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• 2022

Various iron minerals that precipitate in acid mine drainage have a great influence on the concentration change and mobility of trace elements in the drainage during phase transition to other minerals as well as the precipitation process. This study investigated the change of mineral properties and the behaviors of trace elements influenced by pH and time for the precipitates collected from the acid mine drainage treatment system of the Dalsung mine, where schwertmannite is mainly precipitated. However, the main mineral precipitated in the drainage was goethite, suggesting schwetmannite has already undergone a phase transition to goethite to some extent, and it was observed that at higher pH, the peak width at half maximum of XRD peak was narrower. This can be interpreted as the transformation of small amount of amorphous schwetmannite to goethite or an increase in the crystallinity of goethite, and it showed that the higher the pH, the greater this change was. The concentration of Fe was also greatly affected by the pH values, and as the pH increased, the concentration of Fe in the drainage decreased. With increasing time, the Fe concentration increased and then decreased, which can be interpreted to indicate the dissolution of schwertmannite and precipitation of goethite. This mineral change probably resulted in the rapid increase of the concentration of S at initial stage, but its concentration was stabilized later. The concentration of S is also related to the stability of schwetmannite, showing a high concentration at a low pH at which schwertmannite is stable and a low concentration at a high pH at which goethite is stable. The trace elements present as cations in the drainage also showed a close relationship with the pH, generally the lower the pH, the higher the concentration, due to the solubility changes by the pH, and the precipitation and the changes in mineral surface charge at high pH. On the other hand, in the case of As, existing as an anion, although it showed a high concentration at low pH, its concentration increased with time at all pH values, which is probably related to the concentration of Fe which can be coprecipitated in the drainage, and the increase of As concentration with time is also considered to be related to the decrease in schwertmannite rather than the mineral surface charge.

• Economic and Environmental Geology
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• v.56 no.3
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• pp.239-257
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• 2023

Sangdong deposit, a W-Mo skarn deposit, is located in Taebaeksan mineralized district, hosting vertically developed scheelite-quartz veins that formed at the late ore-forming stage. In this study, we tried to examine the geochemical signatures of ore-forming fluids and vein-forming mechanisms by analyzing the micro-texture of quartz veins and trace element concentrations of quartz. As a result of texture analyses, quartz veins in the hanging wall orebody and the foot wall orebody commonly exhibit the blocky and the elongate blocky texture, respectively, whereas quartz veins in the main orebody show both textures. These textural differences indicate that quartz veins from the hanging wall orebody were precipitated by the primary hydrofracturing due to H₂O saturation in the igneous body with relatively high temperature and pressure at a vein-skarn stage, and after that, repeated hydrofracturing caused the formation of quartz veins from the main orebody and foot wall orebody. The results of trace element concentrations show that Li⁺+Al³⁺↔Si⁴⁺ is a main substitution mechanism. However, those of the foot wall orebody were clearly divided into a Li⁺-dominated substitution and a Na⁺-, K⁺-dominated substitution. Considering that quartz veins from the foot wall orebody commonly show the elongate blocky texture, such a distinction means that it is a result of repeated injections of fluid with the different composition. Ti concentrations of quartz from the hanging wall, main, and the foot wall orebody are 28.6, 8.2, and 15.7 ppm in average, respectively. Given a proportional relationship between the precipitation temperature and Ti concentrations, it seems that quartz veins from the hanging wall orebody were precipitated at the highest temperature. Al concentrations of the hanging wall, main, and the foot wall orebody having an inverse relationship with fluid pH are 162.3, 114.2, and 182.5 ppm in average, respectively. These results show that Al concentrations in vein-forming fluids were not changed dramatically. Moreover, these concentrations are extremely low in comparison with the other hydrothermal deposits. This indicates that quartz in overall ore veins at Sangdong deposit was precipitated from the constant condition with slightly acidic to near neutral pH.

• Economic and Environmental Geology
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• v.56 no.3
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• pp.301-310
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• 2023

Ferrihydrite is an iron oxide mineral that is easily found in the natural environment, including acid mine drainage, and has a low crystallinity and high specific surface area, resulting in high reactivity with other ions, and can remove environmentally hazardous substances. However, because ferrihydrite is a metastable mineral, there is a possibility of releasing adsorbed ions by phase transformation to other minerals having low surface area and high crystallinity. In this study, the adsorption characteristics of arsenate, chromate, and selenate on ferrihydrite and the oxyanion removal efficiency of ferrihydrite were studied considering mineral phase transformation. At both pH 4 and 8, the adsorption of oxyanions used in the study were in good agreement with both Langmuir and Freundlich adsorption models except for selenate at pH 8. Due to the difference in surface charge according to pH, at pH 4 a higher amount of ions were adsorbed than at pH 8. The adsorption amount were in the order of arsenate, chromate, and selenate. These different adsorption models and adsorption amounts were due to different adsorption mechanisms for each oxyanions on the surface of ferrihydrite. These adsorption characteristics were closely related to changes in the mineral phase. At pH 4, a phase transformation to goethite or hematite was observed, but only a phase transformation to hematite was observed at pH 8. Among the oxyanion species on ferrihydrite, arsenate showed the highest adsorption capacity and hardly caused phase transformation during the experimental period after adsorption. Contrary to this, chromate and selenate showed faster mineral phase transformation than arsenate, and selenate had the lowest retardation effect among the three oxyanions. Ferrihydrite can effectively remove arsenate due to its high adsorption capacity and low phase transformation rate. However, the removal efficiency for other two oxyanions were low by the low adsorption amount and additional mineral phase transformation. For chromate, the efficient removal is expected only at low concentrations in low pH environments.

• 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.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.24 no.2
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• pp.267-281
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• 2019

Energetic mesoscale eddies in the East Sea (ES) associated with strong mesoscale variability impacting circulation and environments were statistically characterized by analyzing satellite altimeter data collected during 1993-2017 and in-situ data obtained from four cruises conducted between 2015 and 2017. A total of 1,008 mesoscale eddies were detected, tracked, and identified and then classified into 27 groups characterized by mean lifetime (L, day), amplitude (H, m), radius (R, km), intensity per unit area (EI, $cm^2/s^2/km^2$), ellipticity (e), eddy kinetic energy (EKE, TJ), available potential energy (APE, TJ), and direction of movement. The center, boundary, and amplitude of mesoscale eddies identified from satellite altimeter data were compared to those from the in-situ observational data for the four cases, yielding uncertainties in the center position of 2-10 km, boundary position of 10-20 km, and amplitude of 0.6-5.9 cm. The mean L, H, R, EI, e, EKE, and APE of the ES mesoscale eddies during the total period are $95{\pm}104$ days, $3.5{\pm}1.5cm$, $39{\pm}6km$, $0.023{\pm}0.017cm^2/s^2/km^2$, $0.72{\pm}0.07$, $23{\pm}21TJ$, and $588{\pm}250TJ$, respectively. The ES mesoscale eddies tend to move following the mean surface current rather than propagating westward. The southern groups (south of the subpolar front) have a longer L, larger H, R, and higher EKE, APE; and stronger EI than those of the northern groups and tend to move a longer distance following surface currents. There are exceptions to the average characteristics, such as the quasi-stationary groups (the Wonsan Warm, Wonsan Cold, Western Japan Basin Warm, and Northern Subpolar Frontal Cold Eddy groups) and short-lived groups with a relatively larger H, higher EKE, and APE and stronger EI (the Yamato Coastal Warm, Central Yamato Warm, and Eastern Japan Basin Coastal Warm eddy groups). Small eddies in the northern ES hardly resolved using the satellite altimetry data only, were not identified here and discussed with potential over-estimations of the mean L, H, R, EI, EKE, and APE. This study suggests that the ES mesoscale eddies 1) include newly identified groups such as the Hokkaido and the Yamato Rise Warm Eddies in addition to relatively well-known groups (e.g., the Ulleung Warm and the Dok Cold Eddies); 2) have a shorter L; smaller H, R, and lower EKE; and stronger EI and higher APE than those of the global ocean, and move following surface currents rather than propagating westward; and 3) show large spatial inhomogeneity among groups.