• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.355-363
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• 2023

In this study, we explore the nature of clumped isotopes of H₂O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (¹⁶O, ¹⁷O, and ¹⁸O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H₂O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT¹⁸O), 1.16 times (HT¹⁷O), and 0.703 times (HD¹⁷O) relative to HD¹⁸O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H₂O including ¹⁷O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H₂O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

• Radioisotope journal
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• v.13 no.1
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• pp.71-75
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• 1998

• Journal of the Korean Chemical Society
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• v.47 no.3
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• pp.191-198
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• 2003

The pairwise energy model (PEM) assumes that the cross section for the reaction cross section for the reaction A+BC$\{leftrightarrow}$B+C, where B and C are isotopes of hydrogen, depends on only the pairwise relative energy Es between A and B. Until now, the PEM has been used to interpret theoretically the isotope effect for the reactions such as $O(^3P)+HD,\;Ar^++(H_2,\;D_2,and\;HD)$. In this paper we carry out extensive quasiclassical trajectory calculations for the three possible reactions $Cl+H_2$ and HD and show that the PEM works very well at high energy. In particular we are able to accurately predict the intramolecular isotope effect at high energy for the reaction of Cl+HD using only the cross section data for $Cl+H_2$. To understand that the PEM works so well at high energy, the internal energy distributions for the products are examined. The distributions for three reactions are different at a fixed relative collision energy E but are approximately same at a fixed pairwise energy Es. This suggests that the PEM works very well at high energy. We believe the conclusions reached here will apply to other A+BC systems.

• Journal of The Korean Society of Grassland and Forage Science
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• v.36 no.4
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• pp.318-324
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• 2016

In order to study the effect of barley, Italian ryegrass (IRG), and legume mixture on nitrogen fixation and transfer to grasses on spring paddy field, an experiment was carried out from Oct. 2006 to June 2007 in Naju, Korea. A split plot design with three replications was used for the experiment. One reference plot was assigned for each treatment to determine nitrogen fixation. Main plots consisted of Chinese milk vetch, crimson clover, forage pea, and hairy vetch with barley, respectively. Subplot treatment were barley or IRG with four seeding ratio of legumes (50:50, 60:40, 70:30, and 80:20). To estimate N fixation by legumes, $^{15}N$ isotope dilution technique was used. $^{15}N$ fertilizer [$(^{15}NH_4)_2SO_4$ solution at 99.8 atom N] was uniformly applied to $600cm^2$ in the middle of each plot on April 15, 2007. Plots were harvest by hand on June 8, 2007. Dried sample were ground to a fine power and analyzed for total N isotope N. $^{15}N$ was determined using elemental analyzer-isotope ratio mass spectrometry. The calculation of N transfer was determined with the isotope dilution method. The content of N was higher in legumes than that in barley or Italian ryegrass. Nitrogen level in forage pea was significantly higher than that of other legumes. There were significantly differences in N content between legumes in IRG mixture. Atom % $^{15}N$ excess was significantly different in legumes with barley. The 60:40 sub plot had higher (p<0.05) atom % $^{15}N$ than other seeding ratio treatments. The enrichment ranged from 0 to 0.58. Compared to barley, the enrichment of IRG with its accompanied legumes was higher, ranging from 0.38 to 1.0. The N derived from the atmosphere (Ndfa) ranged from 0% to 49.5% with barley-legume mixture. It ranged from 0 to 60.5% in IRG-legume plots. N transfer from legumes to neighboring grasses was 12.3 to 90.9 kg/ha for barley-legume mixture and 31.7 to 107.8 kg/ha for IRG plots. IRG plots showed higher N transfer for IRG-legume mixture in general based on difference method. Based on $^{15}N$ dilution method, the N transfer was 0 to 36.1 kg/ha for barley-legume mixture and 0 to 50.6 kg/ha for IRG plots. There was a tendency toward higher N transfer on the difference method than that of the $^{15}N$ dilution method.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.92-92
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• 2016

전기방전의 기본적인 특성을 가지고 있는 플라즈마를 이용하여 재료를 가공하는 증착, 식각, 표면처리 공정에 있어서 플라즈마 내의 전자 충돌 반응에 의한 이온, 라디칼의 생성과 재료 표면의 반응을 분석하는 도구로써 분압 측정은 일반적인 화학 조성 분석에 기원한 오랜 역사를 가지고 있다. 1 amu 정도의 분해능을 가지고 있고 크기가 30 cm 정도에 불과한 사중극자 질량 분석기는 적절한 질량 스캔 시간과 넓은 이온 전류 측정 범위를 가지므로 소형 차등 배기 시스템과 조합하면 1 mTorr 영역의 스퍼터링 시스템에서 1 Torr 영역의 PECVD/PEALD 시스템 진단에도 쉽게 적용이 가능하다. Inficon사의 CPM-300과 Pfeiffer사의 Prisma80을 이용한 플라즈마 식각 공정 분석 결과를 보면 동위원소까지 분석이 가능하다. 또한 전자충돌 이온화 에너지를 조절하여 m/q(질량전하비율)가 중첩되는 경우의 해석도 가능하다. 다중 오리피스를 갖는 compact design의 밸브 블록을 이용한 설계에서는 line-of-sight 입사가 불가능하여 이온 전류를 분석할 수 없다는 단점이 있으나 표준 가스를 이용한 정량화 등의 큰 장점들이 있다. 최근 이루어진 연구의 내용으로는 유도 결합 플라즈마 장치에서 전도성 메쉬를 이용한 라디칼 거동 관찰을 위해서 두 대의 CPM-300을 메쉬 전 후에 설치하여 라디칼의 양 변화를 전류 프로브와 같이 사용하여 조사하였다.

• Economic and Environmental Geology
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• v.15 no.3
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• pp.155-166
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• 1982

Sulfur isotope compositions (${\delta}^{34}S$) of seventy one sulfide minerals from the Shinyemi ore deposits were determined to range from -10.1 to +5.0‰ with a mean value of +2.1‰. These values are roughly comparable to those of various hydrothermal ore deposits in Korea, about +2.0 to +7.0‰ in ${\delta}^{34}S$, suggesting that they are to be same in source of sulfur. The Shinyemi deposits are grouped into two types; the western bedded skarn orebodies and the eastern small pipes and veins. The ${\delta}^{34}S$ values of sulfide minerals from the bedded orebodies (early mineralization) are ranging from -10.1 to +2.5‰, which is relatively wide in range, whereas those of the pipes and veins. (later mineralization) have a narrow range of ${\delta}^{34}S$ values, +2.7 to +5.0‰, regardless of the kind of sulfide minerals. Isotopic temperature obtained from the sphalerite-galena mineral pairs of the New B orebody appeared to be about 400 to $540^{\circ}C$ are reasonably good agreement with the comparable data of skarn mineral assemblages. It is concluded that the west orebodies were formed in earlier stage at higher temperatures than the east orebodies formed later at lower temperatures. Judging from the various data from the present study, the Shinyemi deposits can be defined as a typical contact metasomatic deposit. The source of sulfur in the hydrothermal solutions is considered to be comagmatic with the Shinyemi granodiorite.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.765-779
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• 2023

The Daum Vent Field (DVF) was newly discovered in the Central Indian Ridge during the hydrothermal expedition by the Korea Institute of Ocean Science & Technology (KIOST) in 2021. In this paper, we describe the detailed mineralogy and geochemistry of hydrothermal chimney and mound to understand the nature of hydrothermal mineralization in the DVF. The mineral assemblages (pyrite±sphalerite±chalcopyrite) of dominant sulfides, FeS contents (mostly <20 mole %) of sphalerite, and (Cu+Zn)/Fe values (0.001-0.22) of bulk compositions indicate that the DVF has an strong affinity with basaltic-hosted seafloor massive sulfide (SMS) deposit along the oceanic ridge. Combined with the predominance of colloform and/or dendritic-textured pyrite and relatively Fe-poor sphalerite in chimneys, the fluid-temperature dependency of trace element systematics (Co, Mn, and Tl) between chimney and mound indicates that the formation of mound was controlled by relatively reducing and high-temperature fluids compared to chimney. The δ³⁴S values (+8.31 to +10.52‰) of pyrite reflect that sulfur and metals were mainly leached from the associated basement rocks (50.6-61.3%) with a contribution from reduced seawater sulfur (38.7-49.4%). This suggests that the fluid-rock interaction, with little effect of magmatic volatile influx, is an important metal source for the sulfide mineralization in the DVF.

• The Journal of the Petrological Society of Korea
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• v.21 no.2
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• pp.235-247
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• 2012

Peridotite xenoliths hosted by alkali basalts from South Korea occur in Baengnyeong Island, Jeju Island, Boeun, Asan, Pyeongtaek and Ganseong areas. K-Ar whole-rock ages of the basaltic rocks range from 0.1 to 18.9 Ma. The peridotites are dominantly lherzolites and magnesian harzburgites, and the constituent minerals are Fo-rich olivine ($Fo_{88.4-92.0}$), En-rich orthopyroxene, Di-rich clinopyroxene, and Cr-rich spinel (Cr# = 7.8-53.6). Hydrous minerals, such as pargasite and phlogopite, or garnet have not been reported yet. The Korean peridotites are residues after variable degree of partial melting (up to 26%) and melt extraction from fertile MORB mantle. However, some samples (usually refractory harzburgites) exhibit metasomatic enrichment of the highly incompatible elements, such as LREE. Equilibration temperatures estimated using two-pyroxene geothermometry range from ca. 850 to $1050^{\circ}C$. Sr and Nd isotopic compositions in clinopyroxene separates from the Korean peridotites show trends between depleted MORB-like mantle (DMM) and bulk silicate earth (BSE), which can be explained by secondary metasomatic overprinting of a precursor time-integrated depleted mantle. The Korean peridotite clinopyroxenes define mixing trends between DMM and EM2 end members on Sr-Pb and Nd-Pb isotopic correlation diagrams, without any corresponding changes in the basement. This is contrary to what we observe in late Cenozoic intraplate volcanism in East Asia which shows two distinct mantle sources such as a DMM-EM1 array for NE China including Baengnyeong Island and a DMM-EM2 array for Southeast Asia including Jeju Island. This observation suggests the existence of large-scale two distinct mantle domains in the shallow asthenosphere beneath East Asia. The Re-Os model ages on Korean peridotites indicate that they have been isolated from convecting mantle between ca. 1.8 and 1.9 Ga.

• Journal of the Mineralogical Society of Korea
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• v.15 no.3
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• pp.205-220
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• 2002

The gold-silver deposits in the Casado district were formed in the sheeted and stockwork quartz veins which fill the fault fractures in volcanic rocks. K-Ar dating of alteration sericite (about 70 Ma) indicates a Late Cretaceous age for ore mineralization. These veins are composed of quartz, adularia, carbonate, and minor of pyrite, sphalerite, chalcopyrite, galena, Ag-sulfosalts (argentite, pearceite, Ag-As-Sb-S system), and electrum. These veins are characterized by chalcedonic, comb, crustiform and feathery textures. Based on the hydrothermally altered mineral assemblages, regional alteration zoning associated with mineralization in the Gasado district is defined as four zones; advanced argillic (kaolin mineral-alunite-quartz), argillic (kaolin mineral-quartz), phyllic (quartz-sericite-pyrite) and propylitic (chlorite-carbonate-quartz-feldspar-pyroxene) zone. Phyllic and propylitic zones is distributed over the study area. However, advanced argillic zone is restricted to the shallow surface of the Lighthouse vein. Compositions of electrum ranges from 14.6 to 53.7 atomic % Au, and the depositional condition for mineralization are estimated in terms of both temperature and sulfur fugacity: T=245。$~285^{\circ}C$, logf $s_2$=$10^{-10}$ ~ $10^{-12}$ Fluid inclusion and stable isotope data show that the auriferous fluids were mixed with cool and dilute (158。~253$^{\circ}C$ and 0.9~3.4 equiv. wt. % NaCl) meteoric water ($\delta^{18}$ $O_{water}$=-10.1~8.0$\textperthousand$, $\delta$D=-68~64$\textperthousand$). These results harmonize with the hot-spring type of the low-sulfidation epithermal deposit model, and strongly suggest that Au-Ag mineralization in the Gasado district was formed in low-sulfidation alteration type environment at near paleo-surface.

• The Korean Journal of Physiology
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• v.22 no.2
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• pp.163-177
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• 1988

The $Ca^{2+}-ATPase$ of sarcoplasmic reticulum (SR) was solubilized and reconstituted into a mixture of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) of varying ratios in order to assess the effect of physical states of phospholipids on the incorporation and functions $Ca^{2+}-ATPase$. On the basis of the spectral data of Ca-arsenazo III, the $Ca^{2+}$ uptake of SR was increased linearly as the PC content increased in the reconstituted vesicles. The ATP hydrolysis activity also increased as PC content increased up to 25% and then decreased slightly as the PC content further increased. On the other hand the incorporation of $Ca^{2+}-ATPase$ into the reconstituted vesicls occured maximally at 25% PC and 75% PE mixture which is known to have a non-bilayer structure in reconstitution system. From the above results it is clear that preexisting defects in the lipid bilayer promote protein incorporation into the bilayer during reconstitution and lamellar structure of the bilayer facilitates the $Ca^{2+}-ATPase$ function.