• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.27 no.3
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• pp.144-157
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• 2022

Noble gases, which are chemically inert and behave conservatively in marine environments, have been used as tracers of physical processes such as air-sea gas exchange, mixing of water masses, and distribution of glacial meltwater in the ocean. For precise measurements of Ne, Ar, and Kr, we developed a mass spectrometric system consisting of a quadrupole mass spectrometer (QMS), a high vacuum preparation line, an activated charcoal cryogenic trap (ACC), and a set of isotope standard gases. The high vacuum line consists of three sections: (1) a sample extraction section that extracts the dissolved gases in the sample and mixes them with the standard gases, (2) a gas preparation section that removes reactive gases using getters and separates the noble gases according to their evaporation points with the ACC, and (3) a gas analysis section that measures concentrations of each noble gas. The ACC attached to the gas preparation section markedly lowered the partial pressures of Ar and CO₂ in the QMS, which resulted in a reduced uncertainty of Ne isotope analysis. The isotope standard gases were prepared by mixing ²²Ne, ³⁶Ar, and ⁸⁶Kr. The amounts of each element in the mixed standard gases were determined by the reverse isotope dilution method with repeated measurements of the atmosphere. The analytical system achieved precisions for Ne, Ar, and Kr concentrations of 0.7%, 0.7%, and 0.4%, respectively. The accuracies confirmed by the analyses of air-equilibrated water were 0.5%, 1.0%, and 1.7% for Ne, Ar, and Kr, respectively.

• Bulletin of the Korean Chemical Society
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• v.23 no.7
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• pp.935-936
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• 2002

• Mass Spectrometry Letters
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• v.5 no.1
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• pp.12-15
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• 2014

Thermal ionization mass spectrometry (TIMS) was used to determine the concentration and isotope ratio of uranium contained in samples of soil and groundwater collected from Korea. Quantification of uranium in ground water samples was performed by isotope dilution mass spectrometry. A series of chemical treatment processes, including chemical separation using extraction chromatography, was applied to the soil samples to extract the uranium. No treatments other than filtration were applied to the groundwater samples. Isotopic analyses by TIMS showed that the isotope ratios of uranium in both the soil and water samples were indistinguishable from those of naturally abundant uranium. The concentration of uranium in the groundwater samples was within the U.S. acceptable standards for drinking water. These results demonstrate the utility of TIMS for monitoring uranium in environmental samples with high analytical reliability.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.440-446
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• 2005

A method is described for the determination of dibutyltin (DBT) in sediment by isotope dilution using liquid chromatography inductively-coupled plasma/mass spectrometry (LC-ICP/MS). To achieve the highest accuracy and precision, special attentions are paid in optimization and evaluation of overall processes of the analysis including extraction of analytes, characterization of the standards used for calibration and LC-ICP/MS conditions. An approach for characterization of natural abundance DBT standard has been developed by combining inductively-coupled plasma/optical emission spectrometry (ICP/OES) and LC-ICP/MS for the total Sn assay and the analysis of Sn species present as impurities, respectively. An excellent LC condition for separation of organotin species was found, which is suitable for simultaneous DBT and tributyltin (TBT) analysis as well as impurity analysis of DBT standards. Microwave extraction condition was also optimized for high efficiency while preventing species transformation. The present method determines the amount contents of DBT in sediments with expanded uncertainty of less than 5% and its result shows high degree of equivalence with reference values of an international inter-comparison and a certified reference material (CRM) within stated uncertainties.

• Analytical Science and Technology
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• v.21 no.6
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• pp.502-509
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• 2008

An ID LC/MS (isotope dilution liquid chromatography/mass spectrometry) was used as a primary method for the quantitative analysis of cholesterol in human serum. The separation of cholesterol was carried out by Thermo ODS hypersil $C^{18}$ column. The mobile phase was 100% methanol, and flow rate was $0.3m{\ell}/min$. Cholesterol and cholesterol-$3,4-13C_2$ were monitored at m/z 369.4 and 371.3, which correspond to $[M-H_2O+H]^+$ respectively. In order to verify the measurement method, NIST SRM 909b was analyzed. The results agreed well with certified values within uncertainty. The four kinds of serum certified reference material were prepared and certified. The repeatabilities of measurement were ranged from 0.1 to 0.8% (RSD), which were relatively good. The reproducibility between independent measurement run was below 0.24% (RSD). The expanded uncertainty was about 1.43% within the 95% confidence interval.

• Mass Spectrometry Letters
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• v.14 no.4
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• pp.178-185
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• 2023

QuEChERS is used worldwide as a universal sample preparation method with many benefits, such as being quick, easy, cheap, effective, rugged and safe. This study examined whether QuEChERS can be employed in isotope dilution mass spectrometry (ID-MS) for accurate analysis of pesticides in food. The ratios of fortified values and measured values of malathion and fenitrothion using the QuEChERS method were compared with those using the solid phase extract (SPE) method which was previously used in this laboratory. The separations of the two pesticides on DB-5MS and VF-1701MS columns were compared. Malathion and fenitrothion were fortified into kimchi cabbage and pretreated with the QuEChERS method and the SPE method. The results obtained using the DB-5MS column varied according to the sample preparation method, column and pesticide level. Using the VF-1701 column, ratios were 98-102% by both QuEChERS and Carb/NH₂ SPE method for all fortification level. Malathion and fenitrothion were fortified into strawberry samples for comparison with kimchi cabbage. The results for the strawberry samples indicated that the ratios were not influenced by the sample preparation methods or GC column. The QuEChERS method could be acceptable in the ID-MS method for pesticide residue analysis in food, however other conditions should be carefully considered for accurate determination, such as the column, amount of analyte and food matrix.

• Analytical Science and Technology
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• v.31 no.6
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• pp.225-231
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• 2018

Benzoic acid, methyl paraben, and butyl paraben are preservatives that have been used in pharmaceutical, cosmetic, and food products. However, as their toxicities for human have been reported, many nations and organizations including Korea have established a regulation limit for thier usage of these preservatives in food products. The present study developed the isotope dilution liquid chromatography mass spectrometry method for accurate determination of three target preseratives in soysauce. In this study, the isotope dilution liquid chromatography mass spectrometry method was developed for accurate determination of three target preservatives in soy sauce. LC separation was optimized considering the pKa of benzoic acid which is lower than those of methyl and butyl parabens. A C18 column was used with 5 mM ammonium acetate and methanol as mobile phases. Mass spectrometry was operated in negative mode and selected reaction monitoring mode (SRM). Soy sauce sample was cleaned-up with C18 SPE cartridge for removing matrix inferences and color material. Optimized conditions and the method were validated with soy sauce reference materials for the analysis of food preservatives from Health Science Authority in Singapore. The measured values of benzoic acid, methyl and butyl paraben agreed well with reference values within their uncertainties.

• Mass Spectrometry Letters
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• v.8 no.3
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• pp.59-64
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• 2017

In clinical diagnosis, it's well known that the abnormal level of uric acid (UA) in human body is implicated in diverse human diseases, for instance, chronic heart failure, gouty arthritis, diabetes, and so on. As a primary method, an isotope dilution mass spectrometry (IDMS) has been used to obtain the accurate quantity of UA in blood or serum and also develop the certificated reference material (CRM) so as to provide a SI-traceability to clinical laboratories. Due to the low solubility of UA in water, an ammonium hydroxide ($NH_4OH$) has been considered as a promising solvent to increase the solubility of UA that enables the preparation of both UA and its isotope standard solution for next IDMS-based absolute quantification. But, because of using this $NH_4OH$ solvent, it gives rise to the unwanted degradation of UA. In this study, we sought to optimize condition for the stability of UA in $NH_4OH$ solution by varying the mole ratios of UA to $NH_4OH$, followed by ID-LC-MRM analysis. In addition, we also inspected minutely the effect of the storage temperatures. Additionally, we also performed the quantitative analysis of UA in the KRISS serum certificated reference material (CRM, 111-01-02A) with diverse mixing ratios of UA to $NH_4OH$ and then compared those values to its certification value. Based on our experiments, adjusting the mole ratio of 1/2 ($UA/NH_4OH$) with the storage temperature of $-20^{\circ}C$ is an effective way to secure both the solubility and stability of UA in $NH_4OH$ solution for next IDMS-based quantification of UA in serum.

• 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 Society of Soil and Groundwater Environment Conference
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• 2002.04a
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• pp.254-257
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• 2002

The purposes of this research are to identify the source and to analyze the pathway of nitrate contamination in "cultural village", Jeungpyeong. In order to examine recharge processes and flow pattern that closely related to the influent of nitrate contaminant, the flow field was simulated and the oxygen and hydrogen stable isotopes were analyzed. The nitrogen isotope was used to delineate contaminant sources. The shallow groundwater was mainly composed of precipitation, but leakage of domestic water and sewage contributed to the recharge. Nitrate contaminants were possibly from the leakage of sewage and animal waste. The nitrate concentration decreased due to dilution by low concentration water.ion water.