• Title/Summary/Keyword: Oxidation behavior

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Mineralogy and Geochemistry of Fault Gouge in Pyrite-rich Andesite (함황철석 안산암 내 단층 비지의 광물학적 및 지구화학적 연구)

  • Park, Seunghwan;Kim, Yeongkyoo
    • Journal of the Mineralogical Society of Korea
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    • v.27 no.4
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    • pp.301-310
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    • 2014
  • To investigate the role of fault gauge in the behavior of heavy metals caused by the acid rock drainage in the area of pyrite-rich andesite, XRD, pH measurement, XRF, SEM-EDS, ICP, and sequential extraction method were used. Bed rock consists of quartz, pyrophyllite, pyrite, illite, and topaz, but the brown-colored fault gouge is composed of quartz, illite, chlorite, smectite, goethite, and cacoxenite. The mineral composition of bed rock suggests that it is heavily altered by hydrothermal activity. The concentrations of heavy metals in the bed rock are as follows, Zn > As > Cu > Pb > Cr > Ni > Cd, and those in fault gouge are As > Zn > Pb > Cr > Cu > Ni > Cd. The concentrations of the heavy metals in the fault gouge are generally higher than those in the bed rock, especially for Pb, As, and Cr, which were more than twice as those in the bed rock. It is believed that the difference in the amount of heavy metals between the bed rock and the fault gouge is mainly due to the existence of goethite which is the main mineral composition in the fault gouge and can play important role in sequestering these metals by coprecipitation and adsorption. The low pH, caused by oxidation of pyrite, also plays significant role in fixation of those metals. It is confirmed that the fractions of labile (step 1) and acid-soluble (step 2), which can be easily released into the environment, were higher in the bed rock. Those fractions were relatively low in fault gauge, suggesting that fault gauge can play important role as a sink of heavy metals to prevent those ones from being released in the area where the acid rock drainage can have an influence.

Interaction of oxygen with the ordered Ni3Al(111) alloy surface: adsorption and oxide islands formation at 800 K and 1000 K (Ordered Ni3Al(111) 합금표면과 산소와의 상호작용 : 800 K와 1000 K에서의 흡착과 oxide islands 형성연구)

  • Kang, B.C.;Boo, J.H.
    • Journal of the Korean Vacuum Society
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    • v.16 no.5
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    • pp.322-329
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    • 2007
  • The interaction of oxygen with the ordered $Ni_3Al(111)$ alloy surface at 800 K and 1000 K has been investigated using LEED, STM, HREELS, UPS, and PAX. The clean $Ni_3Al(111)$ surface exhibits a "$2{\times}2$" LEED pattern corresponding to the ordered bulk-like terminated surface structure. For an adsorption of oxygen at 800 K, LEED shows an unrelated oxygen induced superstructure with a lattice spacing of $2.93\;{\AA}$ in addition to the ($1{\times}1$) substrate spots. The combined HREELS and the UPS data point to an oxygen chemisorption on threefold aluminum sites while PAX confirms an islands growth of the overlayer. Since such sites are not available on the $Ni_3Al(111)$ surface, we conclude the buildup of an oxygen covered aluminum overlayer. During oxygen exposure at 1000 K, however, we observe the growth of ${\gamma}'-Al_2O_3$ structure on the reordered $Ni_3Al(111)$ substrate surface. This structure has been identified by means of HREELS and STM. The HREELS data will show that at 800 K the oxidation shows a very characteristic behavior that cannot be described by the formation of an $Al_2O_3$ overlayer. Moreover, the STM image shows a "Strawberry" structure due to the oxide islands formation at 1000 K. Conclusively, from the oxygen interaction with $Ni_3Al(111)$ alloy surface at 800 K and 1000 K an islands growth of the aluminum oxide overlayer has been found.

Study of Mg2Ni1-xFex Alloys by Mössbauer Resonance (Mössbauer 공명에 의한 Mg2Ni1-xFex 합금의 연구)

  • Song, MyoungYoup
    • Transactions of the Korean hydrogen and new energy society
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    • v.10 no.2
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    • pp.119-130
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    • 1999
  • After preparing $Mg_2Ni_{1-x}{^{57}}Fe_x$(x=0.015, 0.03, 0.06, 0.12 and 0.24) alloys, they were studied by $M{\ddot{o}}ssbauer$ resonance. The $M{\ddot{o}}ssbauer$ spectra of x=0.015 and 0.03 alloys exhibit two doublets (doublet 1, 2). That of x=0.06 alloys shows two doublets (doublet 1,2) and one six-line, and those of x=0.12 and 0.24 alloys have only one six-line. The doublet 1 for x=0.015, 0.03 and 0.06 alloys is considered to result from a fraction of Fe in excess showing a superparamagnetic behavior. The doublet 2 is considered to result from the Fe substituted for Ni in the $Mg_2Ni$ phase. The values of isomer shift 0.24 ~ 0.28 mm/s suggest that the iron exist in the state $Fe^{+3}$. The result that the quadrapole splitting of the doublet 2 is not zero shows that the distribution of electrons around the iron is asymmetric. Their values for the doublet 2, 1.20 ~ 1.38 mm/s, approach the value of quadrapole for the oxidation number +3. The six-line showing the magnetic hyperfine interactions results from the iron which has not substituted the nickel in the $Mg_2Ni$ phase. The $M{\ddot{o}}ssbauer$ spectra of the hydrided alloys with x=0.015 and 0.03 show six-line. This suggests that the iron segregates with the hydriding reaction. The analysis results of the $M{\ddot{o}}ssbauer$ spectrum, the variation of magnetization with magnetic field, Auger electron spectroscopy and electron diffraction show the segregation of Ni and the formation of MgO. This is considered to result from the reaction of the $Mg_2Ni$ phase with the oxygen contained in the hydrogen as impurity.

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Effect of Fe and BO3 Substitution in Li1+xFexTi2-x(PO4)3-y(BO3)y Glass Electrolytes (Li1+xFexTi2-x(PO4)3-y(BO3)y 계 유리 전해질에서 Fe 및 BO3 치환 효과)

  • Choi, Byung-Hyun;Jun, Hyung Tak;Yi, Eun Jeong;Hwang, Haejin
    • Journal of the Korean Electrochemical Society
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    • v.24 no.3
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    • pp.52-64
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    • 2021
  • The effect of Fe and BO3 doping on structure, thermal, and electrical properties of Li1+xFexTi2-x(PO4)3-y(BO3)y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe2+ and Fe3+ ions in Li1+xFexTi2-x(PO4)3-y(BO3)y glass worked as a network modifier (FeO6 octahedra) and also as a network former (FeO4 tetrahedra). In the case of the glass with low substitution of BO3, boron formed (PB)O4 network structure, while boron preferred BO3 triangles or B3O3 boroxol rings with increasing the BO3 content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO3 substitution was increased, while Fe2+ lowered the GTT and raised the CT. The ionic conductivity of Li1+xFexTi2-x(PO4)3-y(BO3)y glass ceramics were 8.85×10-4 and 1.38×10-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.

A Review of the Influence of Sulfate and Sulfide on the Deep Geological Disposal of High-level Radioactive Waste (고준위방사성폐기물 심층처분에 미치는 황산염과 황화물의 영향에 대한 고찰)

  • Jin-Seok Kim;Seung Yeop Lee;Sang-Ho Lee;Jang-Soon Kwon
    • Economic and Environmental Geology
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    • v.56 no.4
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    • pp.421-433
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    • 2023
  • The final disposal of spent nuclear fuel(SNF) from nuclear power plants takes place in a deep geological repository. The metal canister encasing the SNF is made of cast iron and copper, and is engineered to effectively isolate radioactive isotopes for a long period of time. The SNF is further shielded by a multi-barrier disposal system comprising both engineering and natural barriers. The deep disposal environment gradually changes to an anaerobic reducing environment. In this environment, sulfide is one of the most probable substances to induce corrosion of copper canister. Stress-corrosion cracking(SCC) triggered by sulfide can carry substantial implications for the integrity of the copper canister, potentially posing a significant threat to the long-term safety of the deep disposal repository. Sulfate can exist in various forms within the deep disposal environment or be introduced from the geosphere. Sulfate has the potential to be transformed into sulfide by sulfate-reducing bacteria(SRB), and this converted sulfide can contribute to the corrosion of the copper canister. Bentonite, which is considered as a potential material for buffering and backfilling, contains oxidized sulfate minerals such as gypsum(CaSO4). If there is sufficient space for microorganisms to thrive in the deep disposal environment and if electron donors such as organic carbon are adequately supplied, sulfate can be converted to sulfide through microbial activity. However, the majority of the sulfides generated in the deep disposal system or introduced from the geosphere will be intercepted by the buffer, with only a small amount reaching the metal canister. Pyrite, one of the potential sulfide minerals present in the deep disposal environment, can generate sulfates during the dissolution process, thereby contributing to the corrosion of the copper canister. However, the quantity of oxidation byproducts from pyrite is anticipated to be minimal due to its extremely low solubility. Moreover, the migration of these oxidized byproducts to the metal canister will be restricted by the low hydraulic conductivity of saturated bentonite. We have comprehensively analyzed and summarized key research cases related to the presence of sulfates, reduction processes, and the formation and behavior characteristics of sulfides and pyrite in the deep disposal environment. Our objective was to gain an understanding of the impact of sulfates and sulfides on the long-term safety of high-level radioactive waste disposal repository.