• Korean Journal of Environmental Agriculture
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• v.34 no.3
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• pp.230-237
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• 2015

BACKGROUND: To identify the sources of inaccuracy in LC/MS/MS methods used in the routine quantitation of small molecules are described and discussed. METHODS AND RESULTS: Various UPLC coupled to triple quadrupole mass spectrometer and time of flight (TOF) were used to identify the potential sources of inaccuracy and inducing the pitfalls of qualification and quntitation during the veterinary drug residue analysis. Some of stable isotope labelled veterinary drugs, which were used as internal standards, presented "cross-talk", regardless of manufactures of mass spectrometer and types of spectrometer. Group of sulfonamides also presented inaccuracy qualification and quantitation due to the multi-residue analytical method with the same fragment ions at the close retention times. CONCLUSION: The phenomena of "cross-talk" occurring between subsequently monitored transition from stable isotope labelled and isotope non-labelled authentic chemical were identified. To prevent errors and achieve more accurate data during the analysis of small molecules by LC/MS/MS SRM method, Followings should be taken care of and kept checking; purity and concentration of stable isotope as an internal standard, prevention of carry-over during the separation in column, minimizing the ion suppression by matrix effect, identification of retention time, precursor ion and product ion, and full knowledge of data processing including smoothing and peak integration.

• Magazine of the Korean Society of Agricultural Engineers
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• v.43 no.4
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• pp.120-128
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• 2001

Pollution sources and their environmental contributions were investigated to select the best management practices for the effective control of water quality. The nitrogen isotope mass ratio was determined to estimate the nitrate sources and their contribution. Sampling sites were chosen by calculating effluent loads at each watershed. Two liters each of the surface water samples were collected from four sites at Bokha river and two sites and Gwanri river. They were sequentially prepared through distillation method and analyzed using an isotope ratio mass spectrometer(IsoPrime EA). As revealed by the experimental values obtained the mass ratio values ($\delta$$^{5}$ N) of watersheds with a large amount of nonpoint sources were less than +5 an indication that the samples were influenced by chemical fertilizers. However watersheds with large amount of point sources were influenced not only by chemical fertilizers but also by animal and municipal wastes. The mass ratio values of samples generally decreased during rainy days. But during dry days the mass ratio values well-reflected the nitrate sources and the condition of watersheds. Through this study the nitrogen isotope mass ratio has been found to be useful for estimating nitrate sources and their contribution to the rural watersheds.

• Journal of Applied Biological Chemistry
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• v.42 no.4
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• pp.186-190
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• 1999

Isotope ratio ($^{15}N/^{14}N$) and nitrate-nitrogen concentration in groundwater were measured to investigate the effect of chemical fertilizer and livestock manure on temporal variations in nitrate-nitrogen concentration and to estimate the contribution of fertilizer and manure to groundwater contamination by nitrate. Four study wells from a rural area in Kyonggi province were selected. One well was located on an upper site from a livestock feedlot, and the others were situated at lower sites from the feedlot. The ${\delta}^{15}N$ values were analyzed by a stable isotope ratio mass spectrometer (Micromass, VG Optima IRMS). Reproducibility of the method and precision of the mass spectrometer were below 1.0 and 0.1‰, respectively Even though study wells were located at the same area, nitrate-nitrogen concentrations and ${\delta}^{15}N$ values differed and fluctuated during the sampling period. The ${\delta}^{15}N$ values of well located at upper site from the feedlot were extremely variable (-1.48~20.80‰). The ranges of ${\delta}^{15}N$ value of three wells situated at lower sites from the feedlot were 11.83~20.73 (ave. 16.11), 8.90~11.73 (ave.11.01), and 5.29~12.73‰ (ave. 8.21‰) with increasing distance from the feedlot. The average values of contribution proportion of nitrogen derived from livestock manure to nitrate-nitrogen in groundwater were 79% for the well closet to the feedlot, 44% for the well most distant from the feedlot, and 56% for the well in between the two wells.

• 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.

• Economic and Environmental Geology
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• v.40 no.5
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• pp.699-703
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• 2007

Compound-specific isotope analysis (CSIA) by isotope ratio mass spectrometer (IRMS) interfaced with gas chromatography (GC) is a state of the art analytical technique for stable isotopes in earth sciences, environmental sciences and forensics. Since early 1990s, GC-IRMS has been widely used to investigate the authenticity of food in forensic science and to trace the sources of organic contaminants in environmental science. In Korea, a GC-IRMS was firstly installed at the Korea Basic Science Institute (KBSI) in early 2005. In this study, we introduce the GC-IRMS of the KBSI shortly to stimulate various isotope-related researches of Korea, and report preliminary CSIA results for BTEX of different manufacturers.

• Analytical Science and Technology
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• v.26 no.6
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• pp.387-394
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• 2013

We aim to unveil dietary history recorded in Neolithic human bone from Janghang site at Gadeok Island, Busan. Excavation of Janghang site at Gadeok Island from 2010 to 2011 is an outstanding discovery in Korean Neolithic archaeology. A large number of human bones (48 individuals) were found at Janghang site, which is the largest-scale Neolithic cemetery in Korea. We extracted human bone collagen from 10 individuals and stable carbon and nitrogen isotope analysis were carried out using carbon and nitrogen analyzer connected to a continuous-flow isotope-ratio-monitoring mass-spectrometer. Although bone histological analysis shows poor preservation state, stable isotope results correspond well with bone collagen quality indicator, which implies that bone collagen reflects lifetime signature. Stable carbon and nitrogen isotope result indicates highly marinebased diet(${\delta}^{13}$C=$-14.5{\pm}1.3$‰, ${\delta}^{15}$N=$-17.4{\pm}1.7$‰, n=10), however the possible input of terrestrial animal and wild plant cannot be excluded. Our isotopic findings provide an invaluable information on Neolithic subsistence economy in this coastal area. In addition, Janghang site shows specific features in burial methods and burial goods. Two different burial methods of arranging bodies are found with extended burial type and particularly high ratio of flexed burial type. There are also burial goods such as pottery. However, there are no significant isotopic differences according to burial methods and burial goods. Although this is a preliminary study on this site, our research will provide important clues in understanding isotopic dietary history of Korean Neolithic people.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.23 no.1
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• pp.32-48
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• 2018

The mechanisms of $CH_4$ uptake into and release from the ocean are not well understood due mainly to complexity of the biogeochemical cycle and to lack of regional-scale and/or process-scale observations in the marine boundary layers. Without complete understanding of oceanic mechanisms to control the carbon balance and cycles on a various spatial and temporal scales, however, it is difficult to predict future perturbation of oceanic carbon levels and its influence on the global and regional climates. High frequency, high precision continuous measurements for carbon isotopic compositions from dissolved $CH_4$ in the surface ocean and marine atmosphere can provide additional information about the flux pathways and production/consumption processes occurring in the boundary of two large reservoirs. This paper introduces recent advances on optical instruments for real time $CH_4$ isotope analysis to diagnose potential applications for in situ, continuous measurements of carbon isotopic composition of dissolved $CH_4$. Commercially available, three laser absorption spectrometers - quantum cascade laser spectroscopy (QCLAS), off-axis integrated cavity output spectrometer (OA-ICOS), and cavity ring-down spectrometer (CRDS) are discussed in comparison with the conventional isotope ratio mass spectrometry (IRMS). Details of functioning and performance of a CRDS isotope instrument for atmospheric ${\delta}^{13}C-CH_4$ are also given, showing its capability to detect localized methane emission sources.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.25 no.3
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• pp.392-404
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• 2015

Objectives: This study measured and analyzed the concentrations of crystalline silica, elemental carbon and the contribution ratio of pollutants which influence environmental and respiratory disease around the Ansim Briquette Fuel Complex in Daegu, Korea. Methods: We analyzed the crystalline silica and elemental carbon in the air according to FTIR(Fourier Transform Infrared Spectroscopy) and NIOSH(National Institute of Occupation Safety and Health) method 5040, respectively. In addition, lead stable isotopes, and carbon and nitrogen stable isotopes were analyzed using MC-ICP/MS(Multi Collector-Inductively Coupled Plasma/Mass Spectrometer), and IRMS(Isotope Ratio Mass Spectrometer), respectively. Results: The concentration of crystalline silica in the direct exposure area around the Ansim Briquette Fuel Complex was found to be $0.0014{\pm}0.0005mg/Sm^3$, but not to exceed the exposure standards of the ACGIH(American Conference of Governmental Industrial Hygienists). In the case of the autumn, the direct exposure area was found to show a level 2.5 times higher than the reference area, and on the whole, the direct exposure area was found to have a level 1.4 times higher than the reference area. The concentration of elemental carbon in the direct exposure area and in the reference area were found to be $0.0014{\pm}0.0006mg/Sm^3$, and $0.0006{\pm}0.0003mg/Sm^3$, respectively. This study confirmed the contribution ratio of coal raw materials to residentially deposited dusts in the area within 500 meters from the Ansim Briquette Fuel Complex and the surrounding area with a stable isotope ratio of 24.0%(0.7-62.7%) on average in the case of carbon and nitrogen, and 33.9%(26.6-54.1%) on average in the case of lead stable isotopes. Conclusions: This study was able to confirm correlations with coal raw materials used by the Ansim Briquette Fuel Complex and the surrounding area. The concentration of some pollutants, crystalline silica, and elemental carbon emitted to the direct-influence area around the Ansim Briquette Fuel Complex were relatively higher than in the reference area. Therefore, we need to impose continuous and substantive reduction countermeasures in the future to prevent particulate matter and coal raw materials in the study area. It is time for the local government and authorities to prepare active administrative methods such as the relocation of Ansim Briquette Fuel Complex.

• 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.

• Analytical Science and Technology
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• v.18 no.1
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• pp.27-34
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• 2005

$Li_2B_4O_7$ and $Na_2B_4O_7$ were synthesized with boron isotopic standard material for the measurement of boron isotopes of positive ions (PTIMS) such as $Li_2BO_2{^+}$ (mass 56, 57) and $Na_2BO_2{^+}$ (mass 88, 89) instead of boron mass 10 and 11. The negative ions (NTIMS) such as $^{10}BO_2{^-}$ and $^{11}BO_2{^-}$(mass 42와 43) were also measured with the same boron isotopic standard material. The precision and accuracy were compared between each method, and prescan of isobaric effect was studied. Good result was obtained from NTIMS method which provided the stable and enough peak intensities with good precision and accuracy. The measurement of boron isotopes were performed in ground water sample with about 8 ng-B ($5{\mu}L$ sample solution) obtained from IAEA for international inter-comparison analysis. The standard deviation was found to be 0.03%. Boron content of this ground water was measured using the NTIMS-IDMS. The result was $1.65{\pm}0.003ug-B/mL$ which was better precision compared to the ICP-AES result.