• 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 Korean Society on Water Environment
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• v.31 no.2
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• pp.159-165
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• 2015

The organic matter sources of phytoplankton and related environmental factors influencing algal bloom in Paldang reservoir were studied using nitrogen and carbon isotope ratio(${\delta}^{15}N$, ${\delta}^{13}C$). Phytoplankton samples for stable isotope analysis were collected from four points in reservoir using a plankton net. Physicochemical water quality, algal taxa and hydrological data were collected from published monitoring material. Phytoplankton samples were analyzed by IRMS. CN ratio of each sample was very similar to that of phytoplankton from literature cited. ${\delta}^{15}N$ of each sample was decreased during July. Mixing and dilution of nitrogen sources due to increment of influx by concentrated rainfall were considered as the main reason for the decline of ${\delta}^{15}N$. Based on analyzed ${\delta}^{15}N$ value of each sample, nitrogen source of Bughan river sample was presumed to come from soil. The nitrogen sources of Namhan river and Kyeongan stream samples seemed to be sewage or animal waste. Low ${\delta}^{15}N$ value in August (2012) seemed to be influenced by isotope fractionation due to the blooming of nitrogen-fixation blue-green algae (Anabaena spp.). Variation in ${\delta}^{15}N$ values particularly by blue-green algal bloom was considered the important factor for estimating the organic matter sources of phytoplankton.

• Ocean and Polar Research
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• v.38 no.4
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• pp.339-345
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• 2016

Stable water vapor isotopes have been utilized as a tracer for studying atmospheric global circulations, climate change and paleoclimate with ice cores. Recently, since laser spectroscopy has been available, water vapor isotopes can be measured more precisely and continuously. Studies of water vapor isotopes have been conducted over the world, but it is the early stage in south Korea. For vapor isotopes study, a cryogenic sampling device for water vapor isotopes has been developed. The cryogenic sampling device consists of the dewar bottle, filled with extremely low temperature material and impinger connected with a vacuum pump. Impinger stays put in the dewar bottle to change the water vapor which passes through the inside of impinger into the solid phase as ice. The fact that water vapor has not sampled completely leads to isotopic fractionation in the impinger. To minimize the isotopic fractionation during sampling water vapor, we have tested the method using a serial connection with two sets of impinger device in the laboratory. We trapped 98.02% of water vapor in the first trap and the isotopic difference of the trapped water vapor between two impinger were about 20‰ and 6‰ for hydrogen and oxygen, respectively. Considering the amount of water vapor trapped in each impinger, the isotopic differences for hydrogen and oxygen were 0.33‰ and 0.06‰, respectively, which is significantly smaller than the precision of isotopic measurements. This work can conclude that there is no significant fractionation during water vapor trapping.

• Nuclear Engineering and Technology
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• v.55 no.4
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• pp.1476-1484
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• 2023

Laboratory experiments and point monitoring of reservoir sediments have proven that stable sulfate reduction (SSR) can lower the concentrations of toxic metals and sulfate in acidic groundwater for a long time. Here, we hypothesize that SSR occurred during in situ leaching after uranium mining, which can impact the fate of acid groundwater in an entire region. To test this, we applied a sulfur isotope fractionation method to analyze the mechanism for natural attenuation of contaminated groundwater produced by acid in situ leaching of uranium (Xinjiang, China). The results showed that δ³⁴S increased over time after the cessation of uranium mining, and natural attenuation caused considerable, area-scale immobilization of sulfur corresponding to retention levels of 5.3%-48.3% while simultaneously decreasing the concentration of uranium. Isotopic evidence for SSR in the area, together with evidence for changes of pollutant concentrations, suggest that area-scale SSR is most likely also important at other acid mining sites for uranium, where retention of acid groundwater may be strengthened through natural attenuation. To recapitulate, the sulfur isotope fractionation method constitutes a relatively accurate tool for quantification of spatiotemporal trends for groundwater during migration and transformation resulting from acid in situ leaching of uranium in northern China.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.18 no.1
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• pp.40-46
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• 2013

The isotope ratios of $^{13}C/^{12}C$ and $^{18}O/^{16}O$ for a sample in a mass spectrometer are measured relative to those of a pure $CO_2$ reference gas (i.e., laboratory working standard). Thus, the calibration of a laboratory working standard gas to the international isotope scales (Pee Dee Belemnite (PDB) for ${\delta}^{13}C$ and Vienna Standard Mean Ocean Water (V-SMOW) for ${\delta}^{18}O$) is essential for comparisons between data sets obtained by other groups on other mass spectrometers. However, one often finds difficulties in getting well-calibrated standard gases, because of their production time and high price. Additional difficulty is that fractionation processes can occur inside the gas cylinder most likely due to pressure drop in long-term use. Therefore, studies on laboratory production of pure $CO_2$ isotope standard gas from stable solid calcium carbonate standard materials, have been performed. For this study, we propose a method to extract pure $CO_2$ gas without isotope fractionation from a solid calcium carbonate material. The method is similar to that suggested by Coplen et al., (1983), but is better optimized particularly to make a large amount of pure $CO_2$ gas from calcium carbonate material. The $CaCO_3$ releases $CO_2$ in reaction with 100% pure phosphoric acid at $25^{\circ}C$ in a custom designed, evacuated reaction vessel. Here we introduce optimal procedure, reaction conditions, and samples/reactants size for calcium carbonate-phosphoric acid reaction and also provide the details for extracting, purifying and collecting $CO_2$ gas out of the reaction vessel. The measurements for ${\delta}^{18}O$ and ${\delta}^{13}C$ of $CO_2$ were performed at Seoul National University using a stable isotope ratio mass spectrometer (VG Isotech, SIRA Series II) operated in dual-inlet mode. The entire analysis precisions for ${\delta}^{18}O$ and ${\delta}^{13}C$ were evaluated based on the standard deviations of multiple measurements on 15 separate samples of purified $CO_2$. The pure $CO_2$ samples were taken from 100-mg aliquots of a solid calcium carbonate (Solenhofen-ori $CaCO_3$) during 8-day experimental period. The multiple measurements yielded the $1{\sigma}$ precisions of ${\pm}0.01$‰ for ${\delta}^{13}C$ and ${\pm}0.05$‰ for ${\delta}^{18}O$, comparable to the internal instrumental precisions of SIRA. Therefore, we conclude the method proposed in this study can serve as a way to produce an accurate secondary and/or laboratory $CO_2$ standard gas. We hope this study helps resolve difficulties in placing a laboratory working standard onto the international isotope scales and does make accurate comparisons with other data sets from other groups.

• Journal of Astronomy and Space Sciences
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• v.14 no.2
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• pp.297-311
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• 1997

To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures ($30~150^{\circ}C$). Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were performed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.13 no.4
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• pp.348-353
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• 2008

Oxygen isotope has not been used actively in water mass studies because of difficulties on the analysis though it has advantages as a water mass tracer. The most popular method to analysis the oxygen isotope ratio in water samples is equilibration method: isotopic equilibrium of water with $CO_2$ at constant temperature. The precision of oxygen isotope analysis using commercial automatic $H_2O/CO_2$ equilibrator is ${\pm}0.1%o$. This value is not sufficient for studies in open ocean. The object of this study is to improve the analytical precision enough to apply open ocean studies by modification of the instrument. When sample gas is transferred by the pressure difference, the fractionation which is preferential transportation of light isotope can be occurred since the long transportation path between the equilibrator and mass spectrometer. And the The biggest source of error during the analysis is long distance and large volume of the pathway of sample gas between. Therefore, liquid nitrogen trap and high vacuum system are introduced to the system. The precisions of 14 time analysis of same seawater sample are ${\pm}0.081%o$ and ${\pm}0.021%o$ by built-in system and by modified system in this study, respectively.

• Ocean Science Journal
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• v.40 no.3
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• pp.167-176
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• 2005

A time-series sediment trap was deployed at 1,034 m water depth in the eastern Bransfield Strait for a complete year from December 25, 1998 to December 24, 1999. About 99% of total mass flux was trapped during an austral summer, showing distinct seasonal variation. Biogenic particles (biogenic opal, particulate organic carbon, and calcium carbonate) account for about two thirds of annual total mass flux $(49.2\;g\;m^{-2})$, among which biogenic opal flux is the most dominant (42% of the total flux). A positive relationship (except January) between biogenic opal and total organic carbon fluxes suggests that these two variables were coupled, due to the surface-water production (mainly diatoms). The relatively low $\delta^{13}C$ values of settling particles result from effects on C-fixation processes at low temperature and the high $CO_2$ availability to phytoplankton. The correspondingly low $\delta^{l5}N$ values are due to intense and steady input of nitrates into surface waters, reflecting an unlikely nitrate isotope fractionation by degree of surface-water production. The $\delta^{l5}N$ and $\delta^{l3}C$ values of sinking particles increased from the beginning to the end of a presumed phytoplankton bloom, except for anomalous $\delta^{l5}N$ values. Krill and the zooplankton fecal pellets, the most important carriers of sinking particles, may have contributed gradually to the increasing $\delta^{l3}C$ values towards the unproductive period through the biomodification of the $\delta^{l3}C$ values in the food web, respiring preferentially and selectively $^{12}C$ atoms. Correspondingly, the increasing $\delta^{l5}N$ values in the intermediate-water trap are likely associated with a switch in source from diatom aggregates to some remains of zooplankton, because organic matter dominated by diatom may be more liable and prone to remineralization, leading to greater isotopic alteration. In particular, the tendency for abnormally high $\delta^{l5}N$ values in February seems to be enigmatic. A specific species dominancy during the production may be suggested as a possible and speculative reason.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.441-455
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• 2003

The most common water types are found to be Ca-$HCO_3$, Ca-Na-$HCO_3$ and Ca-Na-$HCO_3$-Cl in Gwangju groundwater. Groundwater near the Gwangju stream are characterized Ca-Cl water type, with over 50 mg/L of C1- and 400 ${\mu}$S/cm of EC. The systematic variation of $Cl^-$, $HCO_3^-$,- EC and ${\gamma}^{18}O$ values in groundwater with distance away from drainages is caused by streamwater infiltration. Stable isotope data indicate that ${\gamma}$D and ${\gamma}^{18}O$ values of groundwaters near drainages were enriched by evaporation effect, showing a equation of ${\gamma}$D=7. 1${\times}{\gamma}^{18}O$-1. ${\gamma}^{18}O$ values over -6${\textperthansand}$ are anomalous in the unconfined groundwater zones, which are influenced by the local surface water enriched in $^{18}O$ composition. Groundwater in highland shows remarkably light ${\gamma}^{18}O$ values below -8$\textperthousand$. The infiltration of streamwater is dominant in unconfined alluvium aquifer near drainages. ${\gamma}^{13}$CDIC values (-17.6∼-15.2$\textperthousand$) of groundwaters near drainages revealed that dissolved inorganic carbon (DIC) is predominantly originated from natural soil-derived $CO_2$. ${\gamma}^{15}N$ and ${\gamma}^{18}O$ values of nitrate are 0∼17.0${\textperthansand}$ and 6.6∼17.4${\textperthansand}$, respectively. Relationship between ${\gamma}^{15}N$ and ${\gamma}^{18}O$ shows a systematic isotopic fractionation caused by denitrification of 40∼60%, suggesting that the major source of groundwater nitrate originated from nitrate of soils, and mixing nitrate of soil and sewage or manure.

• Ocean and Polar Research
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• v.41 no.2
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• pp.89-97
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• 2019

Long chain plant waxes (n-alkanes, n-alkanoic acids, and n-alcohols) and their carbon isotopic compositions (${\delta}^{13}C$) in geologic archives are valuable tools for paleovegetation reconstruction. However, the sensitivity of different plant wax constituents to vegetation shift is not well understood. This study explores controls on the variation in ${\delta}^{13}C$ values of long-chain n-alkanes ($C_{27}$ to $C_{33}$) and n-alkanoic acids ($C_{26}-C_{30}$) in the Gulf of Mexico core sediments (ODP 625B) near the Mississippi River delta. n-Alkanoic acids' ${\delta}^{13}C$ values were higher than those of n-alkanes by 1-2‰ on average and such a pattern is the opposite from their isotope fractionation observed in living plants: 1-2‰ smaller in n-alkanes than n-alkanoic acids. We attribute this offset to contributions from aquatic plants or microbes that produce high concentrations of $^{13}C-enriched$ long-chain n-alkanoic acids. The sensitivity of n-alkanes and n-alkanoic acids to vegetation and climate varied among chain lengths. The $n-C_{33}$ alkanes were most sensitive to $C_4$ grassland expansion among n-alkane homologues, while no specific trend was observed in n-alkanoic acids. This is due to the similarity in n-alkanoic acid concentrations between $C_3$ and $C_4$ plants by homologues and low terrestrial plant-derived n-alkanoic acid contributions to the sediments. The results of this study suggest that long chain n-alkanoic acids' ${\delta}^{13}C$ values in sediments may be influenced by contributions from different sources such as aquatic plants or microbial inputs and therefore interpretations regarding this matter should be cautiously formulated. We suggest that there is a need for further studies on characterizing long-chain n-alkanoic acids ($C_{26}-C_{34}$) in aquatic plants and microbes from various climates and environments in order to investigate their production and integration into sedimentary archives.