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Petrochemistry and Environmental Geochemistry of Shale and Coal from the Daedong Supergroup, Chungnam Coal Field, Korea (충남탄전, 대동누층군의 셰일과 탄질암에 관한 암석화학 및 환경지구화학적 특성)

  • Lee, Chan Hee;Lee, Hyun Koo;Kim, Kyoung-Woong
    • Economic and Environmental Geology
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    • v.30 no.5
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    • pp.417-431
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    • 1997
  • Characteristics of sedimentary rocks and enrichment of toxic elements in shale and coal from the Chungnam coal field were investigated based upon geochemistry of major, trace and rare earth elements. Shale and coal of the area are interbedded along the Traissic to the Jurassic Daedong Supergroup, which can be subdivided into grey shale, black shale and coal. The coal had been mined, however all the mines are abandonded due to the economic problems. The shale and coal are characterized by relatively low contents of $SiO_2$, and $Al_2O_3$ and high levels of loss-on-ignition (LOI), CaO and $Na_2O$ in comparison with the North American Shale Composite (NASC). Light rare earth elements (La, Ce, Yb and Lu) are highly enriched with the coal. Ratios of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in shale and coal range from 30.0 to 351.8 and from 4.2 to 106.8, which have partly negative correlations against $SiO_2/Al_2O_3$ (1.24 to 6.06), respectively. Those are suggested that controls of mineral compositions in shale and coal can be due to substitution and migration of those elements by diagenesis and metamorphism. Shale and coal of the area may be deposited in terrestrial basin deduced from high C/S (39 to 895) and variable composition of organic carbon (0.39 to 18.40 wt.%) and low contents of reduced sulfur (0.01 to 0.05 wt.%). These shale and coal were originated from the high grade metamorphic and/or igneous rocks, and the rare earth elements of those rocks are slightly influenced with diagenesis and metamorphism on the basis of $Al_2O_3$ versus La, La against Ce, Zr versus Yb, the ratios of La/Ce (0.38 to 0.85) and Th/U (3.6 to 14.6). Characteristics of trace and rare earth elements as Co/Th (0.07 to 0.86), La/Sc (0.31 to 11.05), Se/Th (0.28 to 1.06), V/Ni (1.14 to 3.97), Cr/V (1.4 to 28.3), Ni/Co (2.12 to 8.00) and Zr/Hf (22.6~45.1) in the shale and coal argue for inefficient mixing of the simple source lithologies during sedimentation. These rocks also show much variation in $La_N/Yb_N$ (1.36 to 21.68), Th/Yb (3.5 to 20.0) and La/Th (0.31 to 7.89), and their origin is explained by derivation from a mixture of mainly acidic igneous and metamorphic rocks. Average concentrations in the shale and coal are As=7.2 and 7.5, Ba=913 and 974, Cr=500 and 145, Cu=20 and 26, Ni=38 and 35, Pb=30 and 36, and Zn=77 and 92 ppm, respectively, which are similar to those in the NASC. Average enrichment indices for major elements in the shale (0.79) and coal (0.77) are lower than those in the NASC. In addition, average enrichment index for rare earth elements in coal (2.39) is enriched rather than the shale (1.55). On the basis of the NASC, concentrations of minor and/or environmental toxic elements in the shale and coal were depleted of all the elements examined, excepting Cr, Pb, Rb and Th. Average enrichment indices of trace and/or potentially toxic elements (As, Cr, Cu, Ni, Pb, U and Zn) are 1.23 to 1.24 for shale and 1.06 to 1.22 for coal, respectively.

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Petrological Study of the Dioritic and Granitic Rocks from Geochang Area (거창 일대에 분포하는 섬록암류와 화강암류에 대한 암석학적 연구)

  • Han, Mi;Kim, Sun-Woong;Yang, Kyoung-Hee;Kim, Jin-Seop
    • The Journal of the Petrological Society of Korea
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    • v.19 no.3
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    • pp.167-180
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    • 2010
  • The geochemical studies on the plutonic rocks of the Geochang, the central part of the Ryongnam massif, were carried out in order to constrain the petrogenesis and the paleotectonic environment. The objects of this study are dioritic rocks, biotite granite and hornblende granite. The modal compositions indicate that the dioritic rocks are quartz diorite, quartz monzodiorite, tonalite, biotite granites are granodiorite, granite and hornblende granites are granite, quartz monzonite, quartz syenite. These rocks belong to the calc-alkaline series. Especially, trace elements such as Sr, Nb, Sr, Ti are depleted, suggesting that these rocks are produced in the subduction zone related to calc-alkaline series. Also, the studied granitic rocks correspond to peraluminous and I-type. Chondrite-normalized REE patterns show that LREE are enriched much more than HREE, and have weak Eu(-) anomaly. It is similar to pattern of Jurassic granitoids in the South Korea. Total REE value of the biotite granite and hornblende granite ranges 76.21~137.05 ppm and 73.84~483.21 ppm, respectively, also $(La/Lu)_{CN}$ value ranges 9.61~36.47 and 7.17~21.85. It is suggest that studied rocks suppor their emplacement at active continental margin. Also, these rocks are derived from magma generated by partial melting of lower continental crust materials.

Characteristics of Element Geochemistry in Ulleung Basin Sediments During the Late Quaternary (제4기 후기 동안 동해 울릉분지 퇴적물내 원소 함량 특성과 기원지 연구)

  • Um, In-Kwon;Choi, Man-Sik;Shin, Hyung-Sun
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.14 no.2
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    • pp.69-79
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    • 2009
  • Major and trace elements were analyzed in three core sediments to investigate geochemical characteristics of East Sea sediments and provenance changes during late Quaternary in Ulleung Basin. Comparing with Yellow and South Sea sediments, contents of major elements were generally similar while contents of trace elements were significantly different. Furthermore, within this basin, there were some variabilities in trace element compositions. In the western slope sediments (WS), Mo was enriched over 6 times as much as other sites. On the other hand, Zr, Nb, Hf and Ta were enriched in basin sediments (Basin), and Ca and Cs were enriched in southern slope sediments (SS). After excluding elements derived from biogenic, authigenic and diagenetic origins, the lithogenic elements (K, Ti, Cs, Zr, Nb, Hf and Ta) could be classified into three groups from the comparison of element/Al ratios among cores. The first group consisted of elements (K and Ti) that showed the nearly similar element/Al ratios among three cores. The second group contained Cs which showed significant difference between two slope sediments. The third group elements (Zr, Nb, Hf and Ta) showed highly enriched in basin relative to both slope areas. The depth profiles of metal/Al ratios in basin sediments provided the following interpretation for the compositions of sediment and their variation. From 10,000 yr B.P. to 7,000 yr B.P. two lithogenic components (volcanic ashes and western slope sediments) were mixed and deposited in the basin. After 7,000 yr B.P., however, southern slope sediments were mixed with volcanic ashes and deposited in basin area. This event of source change is nearly close to inflow period of the Tsushima Warm Current to Ulleung Basin. Thus, it might be suggested that element geochemistry in Ulleung basin sediment indicate the change of current system in the study area.

Oxidation Behavior of Oxide Particle Spray-deposited Mo-Si-B Alloys

  • Park, J.S.;Kim, J.M.;Kim, H.Y.;Perepezko, J.H.
    • Journal of the Korean Society for Heat Treatment
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    • v.20 no.6
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    • pp.299-305
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    • 2007
  • The effect of spray deposition of oxide particles on oxidation behaviors of as-cast Mo-14.2Si-9.6B (at%) alloys at $1200^{\circ}C$ up to for 100 hrs has been investigated. Various oxide powders are utilized to make coatings by spray deposition, including $SiO_2,\;TiO_2,\;ZrO_2,\;HfO_2$ and $La_2O_3$. It is demonstrated that the oxidation resistance of the cast Mo-Si-B alloy can be significantly improved by coating with those oxide particles. The growth of the oxide layer is reduced for the oxide particle coated Mo-Si-B alloy. Especially, for the alloy with $ZrO_2$ coating, the thickness of oxide layer becomes only one fifth of that of uncoated alloys when exposed to in air for 100 hrs. The reduction of oxide scale growth of the cast Mo-Si-B alloy due to oxide particle coatings are discussed in terms of the change of viscosity of glassy oxide phases that form during oxidation at high temperature.

Effects of Ara-C on UV and MMS-induced Excision Repair, Chromosome Aberrations, Sister Chromatid Exchanges and Replication Inhibition (자외선과 MMS에 의한 절제회복, 염색체이상, 자매염색분체 교환 및 복제억제 현상에 미치는 Ara-C의 영향)

  • Park, Kyung-Hee;Park, Sang-Dai
    • The Korean Journal of Zoology
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    • v.23 no.4
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    • pp.203-218
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    • 1980
  • Unscheduled DNA synthesis, chromosome aberrations, sister chromatid exchanges and DNA replication inhibition induced by the combined treatments with ara-C and UV-light or MMS in $HF_1$, CHO and $HelaS_3$ cells were studied, and the results obtained were as follows: (1) Ara-C was found to inhibit UV-or MMS-induced unscheduled DNA synthesis and the inhibitory effect of ara-C was more remarkable in its post-treatment. (2) Ara-C enhanced the rate of chromosome aberrations induced by MMS or UV-light. Post-treatment with ara-C exhibited the synergistic effect on MMS-induced chromosome aberrations mainly by increases of chromatid deletions. (3) Contrarily, ara-C did not increase the rate of sister chromatid exchanges, particularly in the pre-treatment with MMS, although it was found to induce sister chromatid exchanges. (4) The rate of DNA synthesis was declined immediately after are-C treatment and then recovered. The combined treatments with ara-C and UV-light or MMS showed that the initial response on replication inhibition was similar to that of ara-C, but later responses were similar to that of UV-light or MMS treated group.

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A Geochemical Study on Pyrophyllite Deposits and Andesitic Wall-Rocks in the Milyang Area, Kyeongnam Province (경남 밀양지역 납석광상과 안산암질 모암의 지구화학적 연구)

  • Oh, Dae-Gyun;Chon, Hyo-Taek;Min, Kyoung-Won
    • Economic and Environmental Geology
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    • v.25 no.1
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    • pp.27-39
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    • 1992
  • Several pyrophyllite deposits occur around the Milyang area where Cretaceous andesitic rocks and spatially related granitic rocks are widely distributed. Pyrophyllite ores consist mainly of pyrophyllite, and quartz with small amount of sericite, pyrite, dumortierite, and diaspore. The andesitic rocks and spatially related granitic rocks in this area suggest that they could be formed from the same series of a calc-alkaline magma series. The contents of $SiO_2$, $Al_2O_3$, LOI(loss on ignition) are enriched, and $K_2O$, $Na_2O$, CaO, MgO, $Fe_2O_3$ are depleted in altered andesitic rocks and ores. Enrichment of As, Cr, Sr, V, Sb and depletion of Ba, Cs, Ni, Rb, U, Y, Co, Sc, Zn are characteristic during mineralization. The pyrophyllite ores can be discriminated from the altered-and unaltered wall-rocks by an increasing of $(La/Lu)_{cn}$ from 4.18~22.13 to 8.98~55.05. In R-mode cluster analysis, Yb-Lu-Y, La-Ce-Hf-Th-U-Zr, $TiO_2-V-Al_2O_3$, Sm-Eu, $CaO-Na_2O-MnO$, Cu-Zn-Ag, $K_2O-Rb$ are closely correlated. In the discriminant analysis of multi-element data, $P_2O_5$, As, Cr and $Fe_2O_3$, Sr are helpful to identify the ores from the unaltered-and altered wall-rocks. In the factor analysis, the factors of alteration of andesitic rocks and ore mineralization were extracted. In the change of ions per unit volume, $SiO_2$, $Al^{3+}$ and LOI are enriched and $Na^+$, $K^+$, $Ca^{2+}$, $Mg^{2+}$, $Mn^{2+}$ and $Fe^{3+}$ are depleted during the alteration processes. The Milyang and the Sungjin pyrophyllite deposits could be mineralized by hydrothermal alteration in a geochemical condition of low activity ratio of alkaline ions to hydrogen ion with reference to spatially related granitic rocks.

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Petrology of the Bokyeongsa Volcanics in the northeast Gyeongsang Basin (경상분지 동북부 보경사화산암체의 암석학적 연구)

  • Yun, Sung-Hyo;Lee, Moon-Won;Koh, Jeong-Seon;Kim, Young-La;Han, Mi-Kyeong
    • Journal of the Korean earth science society
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    • v.21 no.5
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    • pp.595-610
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    • 2000
  • This study has been designed to elucidate the petrography and geochemical characteristics of the volcanic rocks and focused on petrogenesis and tectonic environment of the Bokyeongsa volcanics in the northeast Gyeongsang Basin. The Bokyeongsa volcanics consist of the Naeyeonsan tuff which include rock fragment plagioclase, quartz and hornblende and pumice showing welded structures, and felsite. According to the petrochemical data, the Naeyeonsan tuff and felsite are in the range of 68${\sim}$71wt% and 77wt% SiO$_2$ content respectively. The Naeyeonsan tuff belongs to dacite/rhyodacite, and felsite to rhyolite. These volcanics rocks belong to the calc-alkaline rock series on the TAS diagram and the AFM diagram. The variations of major elements of the volcanic rocks show that contene of TiO$_2$, Al$_2$ O$_3$, FeO$^T$, MnO, MgO, CaO are inversely proportional to those of SiO$_2$, but contents of K$_2$O are positively. They represent differentiation trend of calc-alkaline rocks series. In spider disgram of MORB-normalized trace element partterns, contents of K, Rb, Th and Ta are relatively high, but those of Nb, Zr, Hf, Ti, Y and Yb are nearly similar to MORB. In the chondrite-normalized REE patterns, light REEs are more enriched than heavy REEs. The trace element composition and REE patterns suggest that they are typical island-arc calc-akaline volcanic rocks formed in the tectonomagmatic environment of subduction zone under continental margin.

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A STUDY OF THE MECHANISM OF IMPROVING ACID RESISTANCE OF BOVINE TOOTH ENAMEL AFTER PULSED Nd-YAG LASER IRRADIATION (펄스형 Nd-YAG 레이저 조사에 의한 법랑질 내산성 증가 기전에 관한 연구)

  • Lee, Young-Soon;Shon, Heung-Kyu
    • Journal of the korean academy of Pediatric Dentistry
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    • v.23 no.3
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    • pp.640-658
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    • 1996
  • The purpose of this study was to examine the mechanism of improving acid resistance of Nd-YAG laser irradiated tooth enamel and determine the most effective energy density for improving acid resistance. The bovine tooth enamel were lased with a pulsed Nd-YAG laser. The energy densities of exposed laser beam were varied from 10 to $70\;J/cm^2$. To investigate the degree of improving acid resistance by irradiation, all the samples were submerged to demineralize in 0.5 N $HClO_4$ solution for 1 minute. After 1 minute, 0.05 % $LaCl_3$ was added to the solution for interrupting the demineralization reaction. The amounts of dissolved calcium and phosphate in the solution were measured by using an atomic absorption spectrophotometer and the UV/VIS spectrophotometer, respectively. To examine the mechanism of improving acid resistance, X-ray diffraction analysis, infrared spectroscopy, and scanning electron microscopy were taken. The X-ray diffraction pattern of the samples were obtained in the $10^{\circ}{\sim}80^{\circ}2{\theta}$ range with $Cu-K{\alpha}$ radiation using M18HF(Mac Science Co.) with X-ray diffractometer operating at 40 KV and 300 mA. The infra-red spectra of the ground samples in 300 mg KBr pellets 10 mm diameter were obtained in the $4000cm^{-1}\;to\;400cm^{-1}$ range using JASCO 300E spectrophotometer. The scanning electron microscopy was carried out using JSM6400(JEOL Co.) with $500{\sim}2000$ times magnification. The results were as follow 1. The concentration of calcium dissolved from laser irradiated enamel with $50J/cm^2$ was significantly lesser than that of unlased control group (p<0.05) 2. From the result of the X-ray diffraction analysis, $\beta$-TCP, which increases acid solubility, was identified in lased enamel but the diffraction peaks of (002) and (004) became sharp with increasing energy density of laser irradiation. This means that the crystals in lased samples were grown through the c-axis and subsequently, the acid solubility of enamel decreased. 3. The a-axis parameter was slightly increased by laser irradiation, whereas the c-axis parameter was almost constant except for a little decrease at $50J/cm^2$. 4. In the infra-red spectra of lased enamels, phosphate bands ($600{\sim}500cm^{-1}$), B-carbonate bands (870, $1415{\sim}1455cm^{-1}$), and A-carbonate band ($1545cm^{-1}$) were observed. The amounts of phosphate bands and the B-carbonate bands were reduced, on the other hand, the amount of the A-carbonate band was increased by increase the energy density. 5. The SEM experiments reveal that the surface melting and recrystallization were appeared at $30J/cm^2$ and the cracks were observed at $70J/cm^2$. From above results, It may be suggested that the most effective energy density for improving acid resistance of tooth enamel with the irradiation of Nd-YAG laser was $50J/cm^2$. The mechanism of improving acid resistance were reduction of permeability due to surface melting and recrystallization of lased enamel and reduction of acid solubility of enamel due to decrease of carbonate content and growth of crystal.

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