• Bulletin of the Korean Chemical Society
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• v.12 no.1
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• pp.101-103
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• 1991

The kinetic isotope effects (KIE) are determined for the reactions of benzyl benzenesulfonates (BBS), ethyl benzenesulfonates (EBS) and phenacyl benzensulfonates (PAB) with deuterated benzylamine nucleophiles. The inverse secondary ${\alpha}$-deuterium KIE observed were somewhat smaller than those for the corresponding reactions with aniline nucleophiles. The primary $KIE_s$ obtained with PAB were slightly greater than those for the corresponding reactions with anilines, which suggested that the inverse secondary KIE is decreased due to a relatively earlier transition state for bond-making with little change in the hydrogen bonding strength to the carbonyl oxygen.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.857-862
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• 2011

Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.

• Korean Journal of Environmental Agriculture
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• v.11 no.1
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• pp.26-40
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• 1992

Cheju Island formed by Quarternary volcanism provides highly permeable hydrogeological environment. To meet the increasing demand of water in the island, many groundwater wells have been developed. The environmental isotopes(oxygen-18, deuterium, tritium) and chemical analysis of water samples from the eastern part of the island were carried out to ascertain whether groundwater in the eastern part of the island was contaminated by sea water. The result of tritium analysis indicated fast infiltration of meteoric water into underground and rapid mixing process between rain water and groundwater. The results of oxygen-18 and deuterium analysis demonstrated that most of the wells in the eastern part of the island were influenced by sea water intrusion. Chemical analysis of water samples revealed that most groundwater in study area were classified into Na-Cl type and showed high chloride/bicarbonate ratios. Sea water intrusion in the northeastern part of the island has proceeded at least 3 km within the coastaline, and in the south eastern part about 700m.

• 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.

• Journal of Soil and Groundwater Environment
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• v.17 no.4
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• pp.51-62
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• 2012

Effects of climate change on groundwater system requires understanding the groundwater system in temporal and spatial scales through the long-term monitoring. In this study, the spatio-temporal variations of groundwater were analyzed through the continuous observation of water level, electrical conductivity (EC) and water temperature with automatic data-loggers and sampling in a Gwangneung catchment, Korea, for the four years from 2008 to 2011. Groundwater monitoring were performed at the nest-type wells, MW1 and MW2, located in upsteam and downstream of the catchment, respectively. During the survey period, both the total amount of annual precipitation and the frequency of concentrated rainfall have increased resulting in the elevation of runoff. Water level of MW1 showed no significant fluctuations even during the rainy season, indicating the confined groundwater system. In contrast, that of MW2 showed clear seasonal changes, indicating the unconfined system. The lag-time of temperature at both wells ranged from one to three months depending on the screened depths. Results of chemical analyses indicated that major water compositions were maintained constantly, except for the EC decreases due to the dilution effect. Values of the stable-isotope ratios for oxygen and deuterium were higher at MW2 than MW1, implying the confined system at the upstream area could be locally developed.

• Economic and Environmental Geology
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• v.49 no.5
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• pp.361-370
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• 2016

It is well known that the inflow of rainwater and the infiltration of groundwater to sewerage (I/I) increase the sewage and burden sewage treatment plants and lower their treatment efficiency. Therefore, it is important to estimate the amount of I/I. In this study, well groundwaters, public water supplies (PWSs), and sewage and rainwater channels were investigated to check whether oxygen and deuterium isotopes could be used as a tool for I/I estimation. This study shows that the isotopic composition of PWS in Jeonju area is very consistent over time and distinctly lighter than the circulating local rainwater (CLR) because it is supplied from Yongdam Dam, which is located about 40 km inland to the east in the mountainous area. Considering the fact that sewage mostly originates from the PWS, we could calculate the amounts of CLR in the sewerage from a monitoring station using unaffected rainwater and tap water as mixing end members. The calculation revealed that the CLR fraction ranged from 50% to 90% depending on observation time. This is well supported by the dilute natures of the sewages at the station. The fraction of PWS in investigated well waters were about 46%, indicating that leaking of PWS is very serious and is an important groundwater source in the study area. Since the infiltration of such groundwater may not alter the isotopic composition of sewage significantly, the actual I/I would be much greater than the calculated ones.

• 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.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.4
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• pp.192-202
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• 1998

We investigated the geochemistry and environmental isotopes of granite-bedrock groundwater in the Yeongcheon diversion tunnel which is located about 300 m below the land surface. The hydrochemistry of groundwaters belongs to the Ca-HCO$_3$type, and is controlled by flow systems and water-rock interaction in the flow conduits (fractures). The deuterium and oxygen-18 data are clustered along the meteoric water line, indicating that the groundwater are commonly of meteoric water origin and are not affected by secondary isotope effects such as evaporation and isotope exchange. Tritium data show that the groundwaters were mostly recharged before pre-thermonuclear period and have been mixed with younger surface water flowing down rapidly into the tunnel along fractured zones. Based on the mass balance and reaction simulation approaches, using both the hydrochemistry of groundwater and the secondary mineralogy of fracture-filling materials, we have modeled the low-temperature hydrogeochemical evolution of groundwater in the area. The results of geochemical simulation show that the concentrations of Ca$\^$2＋/, Na$\^$＋/ and HCO$_3$and pH of waters increase progressively owing to the dissolution of reactive minerals in flow paths. The concentrations of Mg$\^$2＋/ and K$\^$＋/ frist increase with the dissolution, but later decrease when montmorillonite and illitic material are precipitated respectively. The continuous adding of reactive minerals, namely the progressively larger degrees of water/rock interaction, causes the formation of secondary minerals with the following sequence: first hematite, then gibbsite, then kaolinite, then montmorillonite, then illtic material, and finally microcline. During the simulation all the gibbsite is consumed, kaolinite precipitates and then the continuous reaction converts the kaolinite to montmorillonite and illitic material. The reaction simulation results agree well with the observed, water chemistry and secondary mineralogy, indicating the successful applicability of this simulation technique to delineate the complex hydrogeochemistry of bedrock groundwaters.

• Journal of the Korean Society of Groundwater Environment
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• v.6 no.4
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• pp.171-179
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• 1999

The $CO_2$-rich waters in the Chojeong area are characterized by low pH (5.0~5.8), high $CO_2$pressure (about 1 atm) and high amounts of total dissolved iou (up to 989 mg/L) and chemically belong to Ca-HC $O_3$type. The oxygen. deuterium and tritium isotope data indicate that the mixing process occurred between $CO_2$-rich water and surface water and/or shallow groundwaters and also suggest that the $CO_2$-rich water has been derived from meteoric waters. According to $\delta$$^{13}$ C values (-8.6~-5.3$\textperthousand$). the $CO_2$ in the water is attributed from deep seated $CO_2$gas. The high dissolved carbon (-14.4~-6.8$\textperthousand$. $\delta$$^{13}$ C) in groundwater of the granitic terrain might be affected by $CO_2$-rich water, whereas the dissolved carbon (-17.9~-15.2$\textperthousand$. $\delta$$^{13}$ C) in groundwater of the metamorphic terrain is likely controlled by soil $CO_2$ and from the reaction with calcite in phyllite. Sulfur isotope data (＋3.5~＋11.3$\textperthousand$,$\delta$$^{34}$ $S_{SO4}$) also support the mixing process between $CO_2$-rich water and shallow groundwater. Strontium isotopic ratio ($^{87}$ Sr/$^{86}$ Sr) indicates that the $CO_2$-rich water (0.7138~0.7156) is not related to vein calcite (0.7184) of Buak mine or calcite (0.7281~0.7346) in phyllite. By nitrogen isotope ($\delta$$^{15}$ $N_{NO3}$) the sources of nitrogen (up to 55.0 mg/L, N $O_3$) in the $CO_2$-rich water are identified as fertilizer and animal manure. It also indicates the possibility of denitrification during the circulation of nitrogen in the Chojeong area. The possible evolution model of the $CO_2$-rich water based on the hydrochemical and environmental isotopic data was proposed in this study. The $CO_2$-rich waters from the Chojeong area were primarily derived from the reaction with granite by supply of deep seated $CO_2$. and then the $CO_2$-rich water was mixed and diluted with the local groundwater.ter.

• Journal of the Mineralogical Society of Korea
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• v.17 no.1
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• pp.61-73
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• 2004

The purposes of this study are to investigate the occurrence, the hydrochemical characteristics and the origin of the $CO_2$-rich springs from the Kangwon Province, and to reanalyze the previous studied results of other researchers. The $CO_2$-rich water samples were collected at 13 locations in the Kangwon Province. The $CO_2$-rich water shows a high $CO_2$ concentration ($P_{CO2}$ 0.787 to 4.78 atm), weak acidic pHs, electrical conductivity values ranging from 422 to 2,280 $\mu$S/cm, and high Fe and F contents. The chemical compositions of $CO_2$-rich water from this study area are classified into three types; $Ca-HCO_3$, Ca(Na)-$HCO_3$, $Na-HCO_3$ types. The chemical data of $CO_2$-rich waters and their host rocks indicate that $Na-HCO_3$ type water are mainly influenced by biotite, K-feldspar granite, and Ca(Na)-HC $O_3$, type water is chiefly influenced by gneiss and carbonate minerals in granite. F and Fe contents of $CO_2$-rich waters are abundant in $Na-HCO_3$, and $Ca-HCO_3$ types, respectively. The results of this study suggest that the chemical composition $CO_2$-rich water is mainly controlled by the mineralogical composition of aquifer host rocks. Oxygen and deuterium isotope data indicate that $CO_2$-rich water is meteoric origin. The $\delta^{13}$C values (-0.3$\textperthousand$ to -6.2$\textperthousand$ PDB) suggest that dissolved carbonates are mainly derived from a deep-seated $CO_2$ and partly from carbonate minerals.