A post-irradiation annealing study was conducted with use of reactor pressure vessel(RPV) steel A533B Cl.1 base metal irradiated to a dose of 4.84$\times$10$^{18}$ n/$\textrm{cm}^2$ at about 38$0^{\circ}C$. Microhardness and positron annihilation (PA) methods were used to obtain better understanding of the recovery of radiation hardening. Isochronal anneal experiments indicated that two recovery processes occur during annealing of irradiated specimens. The first recovery process occurs in the temperature range of 280-3O5$^{\circ}C$, Michrohardness and positron annihilation (PA) methods were used to obtain better understanding of the recovery of radiation hardening. Isochronal anneal experiments indicated that two recovery processes occur during annealing of irradiated specimens. The first recovery process occurrs in the temperature range of 280-305$^{\circ}C$. The variations of Ip, Iw and R parameters indicated that the formation of vacancy clusters by vacancy agglomeration and the annihilation of monovacancies are the first recovery process. The second recovery process occurs in the range of 405-49$0^{\circ}C$ and positron annihilation parameters measured indicated that the dissolution of carbon atoms decorated around vacancy-type defects and possible precipitates, and the annihilation of monovacancies give rise to the second recovery process. It was further indicated that radiation anneal hardening (RAH) in the range of 305-405$^{\circ}C$ between the temperature ranges for the two processes occurs due to the formation of carbon-decorated vacancy clusters and precipitates. The activation energies, orders of reaction and other characteristics of recovery processes were determined by the Meechan-Brinkman method. The activation energy for the first recovery process was determined as 1.76 eV and that for the second recovery process as 2.00eV. These values are lower than those obtained by other workers. This difference may be attributed to the lower copper content of the RPV steel used in the present study. The order of reaction for the first recovery process was determined as 1.78, while that for the second recovery process as 1.67 Non-integer orders of reaction for recovery processes seem to be attributed to the fact that several mechanisms for the first order and the second order of reaction are compounded in one process. This result also supports for the above conclusions from measurements of PA parameters.
The Kimhae napseok clay deposit was studied to characterize its mineralogy and genesis. Geology of the deposit is composed of Tertiary volcanic rocks and granodiorite. Tertiary volcanic rocks consist of andesitic tuff with minor interstratified tuffaceous shale, and rhyodacitic tuff. The main ore body of 2.4 to 4 m in thickness developed parallel to the bedding of andesitic tuff bed. Its strike and dip are $N70^{\circ}E-N85^{\circ}E$ and $16^{\circ}NW-32^{\circ}NW$, respectively. Two alteration zones; the propylitic zone of albite-epidote-chlorite-quartz assemblage and advanced argillic zone of pyrophyllite-dickite-alunite-diaspore assemblage are developed. Correlation of $SiO_2$ to $Al_2O_3$ shows no relation in propylitic zone, while a negative linear relation in advanced argillic zone. Chemical variation shows that $SiO_2$, $Al_2O_3$, MgO, CaO, $Na_2O$ and $K_2O$ were leached out during hydrothermal alteration. Pyrophyllite, the most abundant mineral in advanced argillic zone, occurs as low temperature 2M polytype. It is closely associated with dickite, diaspore and alunite. The Hinckley index of dickite is 0.83 showing moderate crystallinity. Na content is increasing in the M site with the increasing content of cations in the R-site. the mole percent of Na replacing K in alunite ranges from 53.2 to 71.6. It is also found that pyrophyllite grows in the dissolution site of diaspore. Plagioclase was albitized. Lowering of pH caused mainly by sulfide and sulfate decomposition resulted in preferential leaching of Si. It is inferred that aluminum released from plagioclase in the volcanic rocks as well as from the tuffaceous shale intercalated in andesitic tuff were the main sources of aluminum required for the formation of clay deposit. pH in hydrothermal fluid decreased from propylitic zone to advanced argillic zone with increasing degree of alteration. Based on experimental data reported in the literature and mineral assemblages, the formation temperature of the deposit ranges 270 to $320^{\circ}C$.
Journal of the Korean Society of Groundwater Environment
/
v.7
no.1
/
pp.32-46
/
2000
Hydrogeochemical and isotope ($\delta$$^{18}$ O, $\delta$D, $^3$H, $\delta$$^{13}$ C, $\delta$$^{34}$ S, $^{87}$ Sr/$^{86}$ Sr) studies of various kinds of waters (thermal groundwater, deep groundwater, shallow groundwater, and surface water) from the Yusung area were carried out in order to elucidate their geochemical characteristics such as distribution and behaviour of major/minor elements, geochemical evolution, reservoir temperature, and water-rock interaction of the thermal groundwater. Thermal groundwater of the Yusung area is formed by heating at depth during deep circlulation of groundwater and is evolved into Na-HCO$_3$type water by hydrolysis of silicate minerals with calcite precipitation and mixing of shallow groundwater. High NO$_3$contents of many thermal and deep groundwater samples indicate that the thermal or deep groundwaters were mixed with contaminated shallow groundwater and/or surface water. $\delta$$^{18}$ O and $\delta$D are plotted around the global meteoric water line and there are no differences between the various types of water. Tritium contents of shallow groundwater, deep groundwater and thermal groundwater are quite different, but show that the thermal groundwater was mixed with surface water and/or shallow groundwater during uprising to surface after being heated at depths. $\delta$$^{13}$ C values of all water samples are very low (average -16.3$\textperthousand$%o). Such low $\delta$$^{13}$ C values indicate that the source of carbon is organic material and all waters from the Yusung area were affected by $CO_2$ gas originated from near surface environment. $\delta$$^{34}$ S values show mixing properties of thermal groundwater and shallow groundwater. Based on $^{87}$ Sr/$^{86}$ Sr values, Ca is thought to be originated from the dissolution of plagioclase. Reservoir temperature at depth is estimated to be 100~1$25^{\circ}C$ by calculation of equilibrium method of multiphase system. Therefore, the thermal groundwaters from the Yusung area were formed by heating at depths and evolved by water-rock interaction and mixing with shallow groundwater.
The deep environment and geochemical evolution of the Bugok geothennal waters, located in the Kyeongnam Province, was re-interpreted based on the hydrochemical and isotopic data published by Yun et al. (1998). The geothermal waters of the Bugok area is geochemically divided into three groups; Geothennal water I, II and III groups. Groups I and II are geochemically similar; high temperature (55.2-77.2$^{\circ}$C) and chemically belonging to Na-S04 types. However, pH and Eh values are a little different each other and Group II water is highly enriched in S04 compared to Group I water. Group III water, occurring from peripheral sites of the central part of the geothennal waters, shows temperature range of 29.3 to 47.0$^{\circ}$C and belongs to $Na-HCO_3-S0_4$ types. The deep environment and geochemical evolution of the Bugok geothennal waters, showing the diversity of geochemistry, can be interpreted as follows; I) Descending to great depth of meteoric waters that originated at high elevation and reacting with sediments and/or granites in depth. The $S0_4$ concentration of the waters has been increased by the dissolution of sulfate minerals in sediments. 2) During the continuous descending, the waters has met with the reduction environment, producing the $H_2S$ gas due to sulfate reduction. The waters has been heated up to 130$^{\circ}$C and the extent of water-rock reaction was increased. At this point, pH of waters are increased, S04 concentration decreased and calcite precipitated, therefore, the waters show the $Na-S0_4$ type. 3) Ascending of the geothennal waters along the flow path of fluids and mixing with less-deeply circulated waters. The $S0_4$ concentration is re-increased due to the oxidation of $H_2S$ gas and/or sulfide minerals in sediments. During continuous ascending, these geothennal waters are mixed with shallow groundwater.
Journal of Korean Society of Environmental Engineers
/
v.36
no.7
/
pp.514-520
/
2014
In this study, the production potential of alternative coagulant ($Al_2(SO_4)_3$ solution) having the identical coagulation activity with respect to the commercial coagulant was investigated. The raw material of alternative coagulant was a spent catalyst including aluminium (waste activated alumina) generated in the manufacturing process of the polymer. The alternative coagulant was produced through a series of processes: 1) intense heat and grinding, 2) chemical polymerization and substitution with $H_2SO_4$ solution, 3) dissolution and dilution and 4) settling and separation. To determine the optimal operating conditions in the lab-scale autoclave and dissolver, the content of $Al_2O_3$ in alternative coagulant was analyzed according to changes of the purity of sulfuric acid, reaction temperature, injection ratio of sulfuric acid and water in the dissolver. The results showed that the alternative coagulant having the $Al_2O_3$ content of 7~8% was produced under the optimal conditions such as $H_2SO_4$ purity of 50%, reaction temperature of $120^{\circ}C$, injection ratio of $H_2SO_4$ of 5 times and injection ratio of water of 2.3 times in dissolver. In order to evaluate the coagulation activity of the alternative coagulant, the Jar-test was conducted to the effluent in aerobic reactor. As a result, in both cases of Al/P mole of 1.5 and 2.0, the coagulation activity of the alternative coagulant was higher than that of the existing commercial coagulant. When the production costs were compared between the alternative and commercial coagulant through economic analysis, the production cost reduction of about 50% was available in the case of the alternative coagulant. In addition, it was identified that the alternative coagulant could be applied at field wastewater treatment plant without environmental problem through ecological toxicity testing.
In order to produce raw material powder of advanced magnetic material by spray roasting process, newly modified spray roasting system was developed in this work. In this spray roasting system, raw material solution was effectively atomized and sprayed into the reaction furnace. Also, uniform temperature distribution inside reaction furnace made thermal decomposition process fully completed, and produced powder was effectively collected in cyclone and bag filter. This system equipped with apparatus which can purify hazard produced gas. In this study complex acid solution was prepared by dissolution of mill scale and ferro-Mn into the acid solution, and the pH of this complex acid solution was controlled about to 4. It was conformed that mill scale and ferro-Mn containing a lot of impurities such as $SiO_2$, P and Al could be used as raw material by reducing the impurities content of complex acid solution below 20 ppm. Complex oxide powder of Fe-Mn system was produced by spraying purified complex acid solution into the spray roaster through nozzle, and the variations of produced powder characters were studied by changing he reaction conditions such as reaction temperature, the injection velocity of solution and air, nozzle tip size and concentration of solution. The morphology of produced powder had spherical shape under the most experimental conditions, and concentration of solution. The morphology of produced powder has spherical shape under the most experimental conditions, and the composition and the particle size distribution were almost uniform, which tells the excellence of this spray roasting system. The grain size of most produced powder was below 100 nm. From the above results, it will be possible to produce ultra fine oxide powder from the chloride of Fe, Mn, Ni, Cu and rare earth by using this spray roasting system, and also to produce ultra fine pure metal powder by changing reaction atmosphere.
Occurrence characteristics and existing forms of U-Th containing minerals in KURT (KAERI Underground Research Tunnel) granite are investigated to understand long-term behavior of radionuclides in granite considered as a candidate rock for the geological disposal of high-level radioactive waste. KURT granite primarily consists of quartz, feldspar and mica. zircon, REE(Rare Earth Element)-containing monazite and bastnaesite are also identified. Besides, secondary minerals such as sericite, microcline and chlorite including quartz vein and calcite vein are observed. These minerals are presumed to be accompanied by a post-hydrothermal process. U-Th containing minerals are mainly observed at the boundaries of quartz, feldspar and mica, mostly less than $30{\mu}m$ in size. Quantitative analysis results using EPMA (Electron Probe Micro-Analyzer) show that 74.2 ~ 96.5% of the U-Th containing minerals consist of $UO_2$ (3.39 ~ 33.19 wt.%), $ThO_2$ (41.61 ~ 50.24 wt.%) and $SiO_2$ (15.43 ~ 18.60 wt.%). Chemical structure of the minerals calculated using EPMA quantitative analysis shows that the U-Th minerals are silicate minerals determined as thorite and uranothorite. The U-Th containing silicate minerals are formed by a magmatic and hydrothermal process. Therefore, KURT granite formed by a magmatic differentiation is accompanied by an alteration and replacement owing to a hydrothermal process. U-Th containing silicate minerals in KURT granite are estimated to be recrystallized by geochemical factors and parameters such as temperature, pressure and pH owing to the hydrothermal process. By repeated dissolution/precipitation during the recrystallization process, U-Th containing silicate minerals such as thorite and uranothorite are formed according to the variation in the concentrated amount of U and Th.
This study aims to identify the mineraloical and petrographical characteristics of caprock from drilling cores of Pohang basin as a potential $CO_2$ storage site. Experiments and modeling were conducted in order to investigate the geochemical and mineralogical caprock effects of carbon dioxide. A series of autoclave experiments were conducted to simulate the interaction in the $scCO_2$-caprock-brine using a high pressure and temperature cell at $50^{\circ}C$ and 100 bar. Geochemical and mineralogical alterations after 15 days of $scCO_2$-caprock-brine sample reactions were quantitatively examined by XRD, XRF, ICP-OES investigation. Results of mineralogical studies, together with petrographic data of caprock and data on the physicochemical parameters of brine were used for geochemical modeling. Modelling was carried out using the The Geochemist's Workbench 11.0.4 geochemical simulator. Results from XRD analysis for caprock sample showed that major compositional minerals are quartz, plagioclase, and K-feldspar, and muscovite, pyrite, siderite, calcite, kaolinite and montnorillonite were included on a small scale. Results from ICP-OES analysis for brine showed that concentration of $Ca^{2+}$, $Na^+$, $K^+$ and $Mg^{2+}$ increased due to dissolution of plagioclase, K-feldspar and muscovite. Results of modeling for the period of 100 years showed that the recrystallization of kaolinite, dawsonite and beidellite, at the expense of plagioclase and K-feldspar is characteristic. Volumes of newly precipitation minerals and minerals passing into brine were balanced, so the porosity remained nearly unchanged. Experimental and modeling results indicate the interaction between caprock and $scCO_2$ during geologic carbon sequestration can exert significant impacts in brine pH and solubility/stability of minerals.
Four types of fluid inclusions are trapped within tourmaline from Daeyou pegmatite, Jangsu-Gun, Jeonllabukdo. They range $5{\sim}100\;{\mu}m$ in size and are grouped into I, II, III, and IV based on the phase behavior at the room temperature: (1) Type I inclusions are liquid-rich and NaCl equivalent salinity ranged $0{\sim}12\;wt%$, and the homogenization temperatures (Th) ranged $181{\sim}230^{\circ}C$ with eutectic temperatures (Te) $-54{\sim}-22^{\circ}C$. (2) Type II inclusions are vapor-rich and salinity ranged $3{\sim}8\;wt%$ NaCl, and Th ranged $177{\sim}304^{\circ}C$ also showing Te $-54{\sim}-29^{\circ}C$. (3) Type III inclusions contain a halite daughter mineral with $31{\sim}40\;wt%$ NaCl, Th $230{\sim}328^{\circ}C$. More than 90% of Type III homogenize by halite dissolution and are spatially associated with silicate melt inclusions. (4) Type IV inclusions are $CO_{2}$-bearing containing various daughter minerals such as sylvite and/or halite. The density of $CO_{2}$ system within the Type IV is $0.80{\sim}0.75\;g/cm^{3}$, Th $190{\sim}317^{\circ}C$, and salinity $2{\sim}35\;wt%$ NaCl. Type III fluid inclusions, considered as the earliest fluid, formed from the fluid exsolved from the crystallizing pegmatite. It is suggested that Type II fluid in the central part of tourmaline were exsolved earlier than Type I fluids in the margin indicating salinity fluctuation during the growth of tourmaline. It implies the fluctuation of the pressure since the salinity of fluid exsolved from the crystallizing melt is governed by the pressure. The last fluid was Type IV, which may be derived from the nearby limestone and metasedimentary rocks. It is suggested that Daeyou pegmatite containing muscovite without miarolitic cavities was formed by the partial melting resulted from the regional metamorphism. Subsequently, the exsolving fluids from the crystallizing melt were trapped in tourmaline at high pressure condition. The exsolved fluids contain various components such as $CaCl_{2}\;and\;MgCl_{2}$ as well as NaCl and KCl. The exsolution began at least at $2.7{\sim}5.3\;kbar\;and\;230{\sim}328^{\circ}C$ with the pressure fluctuation.
Chungkook-Jang was produced by fermenting Bacillus licheniformis CN-115. The changes of chemical composition, enzyme activity, and amino acids during the fermentation were investigated. The proximate composition was shown irregular fluctuation phenomenon during the fermentation, but only the moisture tended some reducing during the fermentation just after steaming. The content of amino nitrogen was increased radically after the 36 hours of fermentation and became the highest level at 18.072 mg/g at the 60 hours of it. In accordance with the fermentation of Chungkook-Jang, pH got to the 8.39 at 60 hours with increasing, protease activity was increased according to the fermentation and acid and neutral protease activity was reduced after being reached at the highest activity at 48 hours. The most suitable pH was 6.5 and temperature was $35^{\circ}C$ for dissolution-activated of protein in the process of fermentation of Chungkook-Jang. The content of water soluble protein and the content of salt soluble protein were increased at continuously according to the fermentation time of Chungkook-Jang the largest quantity. The molecular weight of water soluble protein of Chungkook-Jang fermented for 48 hours was about 19,000. The amino acids of water soluble protein just after steaming were totally 16 kinds and proline was amino acid and them was in series by glutamic acid and serine in that ordered. The amino acids salt soluble protein, just after steaming were totally 16 kinds and was the largest quantity phenylalanine, glutamic acid and aspartic acid and aspartic acid in that order.
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