• Title/Summary/Keyword: Oxygen-Rich

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Preparation and Characterization of $Cu/Ce_xZr_{1-x}O_2$ Catalysts for Preferential Oxidation of Carbon Monoxide (일산화탄소의 선택적 산화반응을 위한 $Cu/Ce_xZr_{1-x}O_2$ 촉매의 합성과 특성분석)

  • Lee, So-Yeon;Lee, Suk-Hee;Cheon, Jae-Kee;Woo, Hee-Chul
    • Clean Technology
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    • v.13 no.1 s.36
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    • pp.54-63
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    • 2007
  • Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.

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Geochemical Equilibria and Kinetics of the Formation of Brown-Colored Suspended/Precipitated Matter in Groundwater: Suggestion to Proper Pumping and Turbidity Treatment Methods (지하수내 갈색 부유/침전 물질의 생성 반응에 관한 평형 및 반응속도론적 연구: 적정 양수 기법 및 탁도 제거 방안에 대한 제안)

  • 채기탁;윤성택;염승준;김남진;민중혁
    • Journal of the Korean Society of Groundwater Environment
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    • v.7 no.3
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    • pp.103-115
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    • 2000
  • The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.

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Geochemistry and Genesis of the Guryonsan(Ogcheon) Uraniferous Back Slate (구룡산(九龍山)(옥천(決川)) 함(含)우라늄 흑색(黑色) 점판암(粘板岩)의 지화학(地化學) 및 성인(成因))

  • Kim, Jong Hwan
    • Economic and Environmental Geology
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    • v.22 no.1
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    • pp.35-63
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    • 1989
  • Geochemical characteristics of the Guryongsan (Ogcheon) uraniferous black slate show that this is an analogue to the conventional Chattanooga and Alum shales in occurrences. Whereas, its highest enrichment ratio in metals including uranium, among others, is explained by the cyclic sedimentation of the black muds and quartz-rich silts, and the uniform depositional condition with some what higher pH condition compared to the conditions of the known occurrences. The cyclic sedimentation, caused by the periodic open and close of the silled basin, has brought about the flush-out) of the uranium depleted water and the recharge with the new metal-rich sea water, which consequently contributed to the high concentration of metals in mud. The metal-rich marine black muds, which mostly occur in the early to middle Palaeozoic times, is attributed by the geologic conditions which related to the atmospheric oxygen contents, and these are scarcely met in the late Precambrian and/or with the onset of Palaeozoic era in the geologic evolution of the earth.

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Trophic State Index (TSI) and Empirical Models, Based on Water Quality Parameters, in Korean Reservoirs (우리나라 대형 인공호에서 영양상태 평가 및 수질 변수를 이용한 경험적 모델 구축)

  • Park, Hee-Jung;An, Kwang-Guk
    • Korean Journal of Ecology and Environment
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    • v.40 no.1
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    • pp.14-30
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    • 2007
  • The purpose of this study was to evaluate trophic conditions of various Korean reservoirs using Trophic State Index (TSI) and predict the reservoir conditions by empirical models. The water quality dataset (2000, 2001) used here were obtained from the Ministry of Environment, Korea. The water quality, based on multi-parameters of dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (TP), total nitrogen (TN), suspended solid (SS), Secchi depth (SD), chlorophyll-${\alpha}$ (CHL), and conductivity largely varied depending on the sampling watersheds and seasons. In general, trophic conditions declined along the longitudinal axis of headwater-to-the dam and the largest seasonal variations occurred during the summer monsoon of July-August. Major inputs of TP occurred during the monsoon (r=0.656, p=0.002) and this pattern was similar to solid dynamics of SS (r=0.678, p<0.001). Trophic parameters including CHL, TP, SD, and TN were employed to evaluate how the water systems varies with season. Trophic State Index (TSI, Carlson, 1977), based on TSI (CHL), TSI (TP), and TSI (SD), ranged from mesotrophic to eutrophic. However, the trophic state, based on TSI (TN), indicated eutrophic-hypereutrophic conditions in the entire reservoirs, regardless of the seasons, indicating a N-rich system. Overall, nutrient data showed that phosphorus was a primary factor regulating the trophic state. The relationships between CHL (eutrophication index) vs. trophic parameters (TN, TP, and SD) were analysed to develop empirical models which can predict the trophic status. Regression analyses of log-transformed seasonal CHL against TP showed that the value of $R^2$ was 0.31 (p=0.017) in the premonsoon but was 0.69 (p<0.001) during the postmonsoon, indicating a greater algal response to the phosphorus during the postmonsoon. In contrast, SD had reverse relation with TP, CHL during all season. TN had weak relations with CHL during all seasons. Overall, data suggest that TP seems to be a good predictor for algal biomass, estimated by CHL, as shown in the empirical models.

The Role of Pulmonary Capillary Pressure in the Oxygen Free Radical-Induced Acute Lung Injury (산소기에 의한 급성 폐손상에서 폐모세혈관압의 역할에 관한 연구)

  • Yoo, Chul-Gyu;Kim, Young-Whan;Han, Sung-Koo;Shim, Young-Soo;Kim, Keun-Youl;Han, Yong-Chol
    • Tuberculosis and Respiratory Diseases
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    • v.39 no.6
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    • pp.474-483
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    • 1992
  • Background: Regardless of its causes, acute lung injury is characterized pathophysiologically by increased pulmonary arterial pressure and the protein-rich edema. Many inflammatory mediators are known to be involved in the pathogenesis of acute lung injury, including oxygen free radicals (OFR). But the changes in pulmonary capillary pressure in the OFR-induced acute lung injury is not clear. While the pulmonary edema characterized by the movement of fluid and solutes is dependent on the pressure gradient and the alveolar-capillary permeability, the role of pulmonary capillary pressure in the development of pulmonary edema is also not well understood. Method: Male Sprague-Dawley rats were divided into 5 groups: normal control (n=5), xanthine/xanthine oxidase (X/XO)-treated group (n=7), catalase-pretreated group (n=5), papaverine-pretreated group (n=7), and indomethacin-pretreated group (n=5). In isolated perfused rat lungs, the sequential changes in pulmonary arterial pressure, pulmonary capillary pressure by double occlusion method, and lung weight as a parameter of pulmonary edema were determined. Results: Pulmonary arterial pressure and pulmonary capillary pressure were increased by X/XO. This increase was significantly attenuated by catalase and papaverine, but indomethacin did not prevent the X/XO-induced increase. Lung weight gain was also observed by X/XO perfusion. It was prevented by catalase. Papaverine did not completely block the increase, but significantly delayed the onset. Indomethacin had no effect on the increase in lung weight. Conclusion: These data suggest that increased pulmonary capillary pressure by OFR may aggravate pulmonary edema in the presence of increased alveolar-capillary permeability and this may not be mediated by cyclooxygenase metabolites.

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Fluid Inclusion and Stable Isotope Studies of the Kwangsin Pb-Zn Deposit (광신 연 - 아연 광상의 유체포유물 및 안정동위원소 연구)

  • Choi, Kwang-Jun;Yun, Seong-Taek;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.30 no.6
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    • pp.505-517
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    • 1997
  • Lead and zinc mineralization of the Kwangsin mine was formed in quartz and carbonate veins that filled fault-related fractures in the limestone-rich Samtaesan Formation of the Chosun Supergroup and the phyllite-rich Suchangni Formation of unknown age. A K-Ar date of alteration sericite indicates that the Pb-Zn mineralization took place during Late Cretaceous (83.5 Ma), genetically in relation to the cooling of the nearby Muamsa Granite (83~87 Ma). Mineral paragenesis can be divided into three stages (I, II, III): (I) the deposition of barren massive white quartz, (II) the main Pb-Zn mineralization with deposition of white crystalline quartz and/or carbonates (rhodochrosite and dolomite), and (III) the deposition of post-ore barren calcite. Mineralogic and fluid inclusion data indicate that lead-zinc minerals in middle stage II (IIb) were deposited at temperatures between $182^{\circ}$ and $276^{\circ}C$ from fluids with salinities of 2.7 to 5.4 wt. % equiv. NaCl and with log $fs_2$ values of -15.5 to -11.8 atm. The relationship between homogenization temperature and salinity data indicates that lead-zinc deposition was a result of fluid boiling and later meteoric water mixing. Ore mineralization occurred at depths of about 600 to 700 m. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S_{CDT}=9.0{\sim}14.5$ ‰) indicate a relatively high ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids (up to 14 ‰), likely indicating an igneous source of sulfur largely mixed with an isotopically heavier sulfur source (possibly sulfates in surrounding sedimentary rocks). There is a remarkable decrease of calculated ${\delta}^{18}O$ value of water in hydrothermal fluids with increasing paragenetic time: stage I, 14.6~10.1 ‰; stage IIa, 5.8~2.2 ‰; stage IIb, 0.8~2.0 ‰; stage IIc, -6.1~-6.8 ‰, This indicates a progressive increase of meteoric water influx in the hydrothermal system at Kwangsin. Measured and calculated hydrogen and oxygen isotope values indicate that the Kwangsin hydrothermal fluids was formed from a circulating (due to intrusion of the Muamsa Granite) meteoric waters which evolved through interaction mainly with the Samtaesan Formation (${\delta}^{18}O=20.1$ to 24.9 ‰) under low water/rock ratios.

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Geochemistry of Geothermal Waters in Korea: Environmental Isotope and Hydrochemical Characteristics I. Bugok Area (한반도 지열수의 지화학적 연구: 환경동위원소 및 수문화학적 특성 I. 부곡 지역)

  • Yun, Seong-Taek;Koh, Yong-Kwon;Kim, Chun-Soo;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.31 no.3
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    • pp.185-199
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    • 1998
  • Hydrogeochemical and environmental isotope studies were undertaken for various kinds of water samples collected in 1995-1996 from the Bugok geothermal area. Physicochemical data indicate the occurrence of three distinct groups of natural water: Group I ($Na-S0_4$ type water with high temperatures up to $77^{\circ}C$, occurring from the central part of the geothermal area), Group II (warm $Na-HCO_{3}-SO_{4}$ type water, occurring from peripheral sites), Group III ($Ca-HCO_3$ type water, occurring as surface waters and/or shallow cold groundwaters). The Group I waters are further divided into two SUbtypes: Subgroup Ia and Subgroup lb. The general order of increasing degrees of hydrogeochemical evolution (due to the degrees of water-rock interaction) is: Group III$\rightarrow$Group II$\rightarrow$Group I. The Group II and III waters show smaller degrees of interaction with rocks (largely calcite and Na-plagioclase), whereas the Group I waters record the stronger interaction with plagioclase, K-feldspar, mica, chlorite and pyrite. The concentration and sulfur isotope composition of dissolved sulfate appear as a key parameter to understand the origin and evolution of geothermal waters. The sulfate was derived not only from oxidation of sedimentary pyrites in surrounding rocks (especially for the Subgroup Ib waters) but also from magmatic hydrothermal pyrites occurring in restricted fracture channels which extend down to a deep geothermal reservoir (typically for the Subgroup Ia waters). It is shown that the applicability of alkaliion geothermometer calculations for these waters is hampered by several processes (especially the mixing with Mg-rich near-surface waters) that modify the chemical composition. However, the multi-component mineral/water equilibria calculation and available fluid inclusion data indicate that geothermal waters of the Bugok area reach temperatures around $125^{\circ}C$ at deep geothermal reservoir (possibly a cooling pluton). Environmental isotope data (oxygen-18, deuterium and tritium) indicate the origin of all groups of waters from diverse meteoric waters. The Subgroup Ia waters are typically lower in O-H isotope values and tritium content, indicating their derivation from distinct meteoric waters. Combined with tritium isotope data, the Subgroup Ia waters likely represent the older (at least 45 years old) meteoric waters circuated down to the deep geothermal reservoir and record the lesser degrees of mixing with near-surface waters. We propose a model for the genesis and evolution of sulfate-rich geothermal waters.

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Revealing the Paleo-ocean Environment of OSM-XX in the Western Pacific Magellan Seamount with Mineralogical and Geochemical Properties of Ferromanganese Crust (서태평양 마젤란해산군 OSM-XX 해저산 망간각의 광물학적, 지화학적 특성과 고해양 고환경 복원 연구)

  • Jinsub Park;Kiho Yang
    • Economic and Environmental Geology
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    • v.56 no.1
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    • pp.55-63
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    • 2023
  • Variations in geochemical and mineralogical properties of the ferromanganese(Fe-Mn) crust reflect environmental changes. In the present study, geochemical and mineralogical analyses, including micro X-ray fluorescence and X-ray diffraction, were utilized to reconstruct the paleo-ocean environment of western Pacific Magellan seamount cluster. Samples of the Fe-Mn crust were collected using an epibenthic sledge from the open seamount XX (151° 51.12' 7.2" E and 16° 8.16' 9.6" N, 1557 meters below sea level) in the Western Pacific Magellan Seamount. According to the structure and phosphating status, the Fe-Mn crust of the OSM-XX can be divided into the following: phosphatizated (L4-L5), massive non-phosphatizated (L3), and porous non-phosphatizated (L1-L2) portions. All ferromanganese layers contain vernadite, and owing to the presence of carbonate fluorapatite (CFA), the phosphatizated portion (L4-L5) is rich in Ca and P. The massive non-phosphatizated section (L3) contains high Mn, Ni, and Co, whereas the porous non-phosphatizated portion (L1-L2), which comprises detrital quartz and feldspar, is rich in Fe. Variations in properties of the Fe-Mn crust from the OSM-XX reflect changes in the nearby marine environment. The formation of this crust started at approximately 51.87 Ma, and precipitation of the CFA during the global phosphatization event that occurred at approximately 36-32 Ma highlights an elevated sea level and low temperature during the associated period. The high Mn, Ni, and Co concentrations and elevated Mn/Fe ratios of samples from the massive phosphatizated portion indicate that the oxygen minimum zone (OMZ) was enhanced, and reducing conditions prevailed during the crust formation. The high Fe and low Mn/Fe ratios in the porous portion indicate a weak OMZ and dominantly oxidizing conditions. These data reflect environmental changes following the end of the Mi-1 glacial period in the Miocene-Oligocene boundary. Subsequently, Mn/Fe and Co/Mn ratios increased slightly in the outermost part of Fe-Mn crust because of the enhanced bottom current and OMZ associated with the continued cooling from approximately 9 Ma. However, the reduced carbonate dissolution rate in the Pacific Ocean from approximately 6 Ma decreased the growth rate of the Fe-Mn crust.

Deformation Characteristics of Zircaloy-4 Fuel Cladding due to Oxidation in Environment of High Temperature and Steam (고온, 수증기 속에서 산화된 질칼로이-4 핵연료 피복관의 변형 특성에 관한 연구)

  • Jung, Sung-Hoon;Suh, Kyung-Soo;Kim, In-Sup
    • Nuclear Engineering and Technology
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    • v.18 no.3
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    • pp.218-227
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    • 1986
  • Studies were conducted to determine the extent of oxidation and same of the mechanical property changes of Zircaloy-4 fuel cladding after it was exposed to hot steam environment. The purpose of these tests was to provide some informations on the embrittlement behavior of CANDU type fuel cladding, which could be experienced under the loss-of-coolant accident conditions. The Zircaloy fuel cladding tubes were exposed in a steam environment at the temperature of 90$0^{\circ}C$, 1,00$0^{\circ}C$. The growth of the ZrO$_2$ layer combined with an oxygen rich $\alpha$-phase layer into the Zircaloy tube material was found as a function of time t and temperature of steam exposure, E=1.1√Dt+0.002 where D is a temperature dependent diffusion coefficient. The tensile strength of the specimens exposed for a short period increased but decreased continuously with further exposure. The circumferential elongation was drastically changed with the exposure time while the hoop strength did't decrease greatly. The X-ray measurement of preferred orientation of the Zircaloy tube material indicated that grains in the as received tube were oriented such that the poles of the basal (0001) planes were predominantly radial, while the poles of the basal plane in the tube materials heattreated at 1,00$0^{\circ}C$ were oriented tangentially. It appears that this reoriented texture may contribute to lessening the decrease of the hoop strength of the heat treated Zircaloy tube material.

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Microstructure and Electrical Properties of ZnO-Zn2BiVO6-Mn3O4 Varistor (ZnO-Zn2BiVO6-Mn3O4 바리스터의 미세구조와 전기적 특성)

  • Hong, Youn-Woo;Ha, Man-Jin;Paik, Jong-Hoo;Cho, Jeong-Ho;Jeong, Young-Hun;Yun, Ji-Sun
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.31 no.5
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    • pp.313-319
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    • 2018
  • This study introduces a new investigation report on the microstructural and electrical property changes of $ZnO-Zn_2BiVO_6-Mn_3O_4$ (ZZMn), where 0.33 mol% of $Mn_3O_4$ and 0.5 mol% of $Zn_2BiVO_6$ were added to ZnO (99.17 mol%) as liquid phase sintering aids. $Zn_2BiVO_6$ contributes to the decrease of sintering temperatures by up to $800^{\circ}C$, and segregates its particles at the grain boundary, while $Mn_3O_4$ enhances ${\alpha}$, the nonlinear coefficient, of varistor properties up to ${\alpha}=62$. In comparison, when the sintering temperature is increased from $800^{\circ}C$ to $1,000^{\circ}C$, the resistivity of ZnO grains decreases from $0.34{\Omega}cm$ to $0.16{\Omega}cm$, and the varistor property degrades. Oxygen vacancy ($V_o^{\bullet}$) (P1, 0.33~0.36 eV) is formed as a dominant defect. Two different kinds of grain boundary activation energies of P2 (0.51~0.70 eV) and P3 (0.70~0.93 eV) are formed according to different sintering temperatures, which are tentatively attributed to be $ZnO/Zn_2BiVO_6$-rich interface and ZnO/ZnO interface, respectively. Accordingly, this study introduces a progressive method of manufacturing ZnO chip varistors by way of sintering ZZMn-based varistor under $900^{\circ}C$. However, to procure a higher reliability, an in-depth study on the multi-component varistors with double-layer grain boundaries should be executed.