• Title/Summary/Keyword: Stable isotope ratio mass spectrometer

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Identification of the Sources of Nitrate using Stable Isotope Mass Ratio in Rural Watersheds (안정 동위원소비를 이용한 농촌하천유역 질산성 질소의 오염원 추정)

  • 홍영진;권순국;홍성구
    • 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.

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Temporal Variations in Isotope Ratios and Concentrations of Nitrate-nitrogen in Groundwater as Affected by Chemical Fertilizer and Livestock Manure

  • Yoo, Sun-Ho;Choi, Woo-Jung;Han, Gwang Hyun;Park, Jung-Geun;Lee, Sang-Mo;Jin, Sheng-ai
    • 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.

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First GC-IRMS in Korea and Its Application Fields (국내 최초로 도입된 GC-IRMS와 응용분야 소개)

  • Shin, Woo-Jin;Lee, Kwang-Sik;Ko, Kyung-Seok
    • 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.

Improvement of Oxygen Isotope Analysis in Seawater samples with Stable Isotope Mass Spectrometer (질량분석기를 이용한 해수 중 산소안정동위원소 분석법의 개선)

  • Park, Mi-Kyung;Kang, Dong-Jin;Kim, Kyung-Ryul
    • 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.

Exposure Assessments of Environmental Contaminants in Ansim Briquette Fuel Complex, Daegu(III) - Contribution and distribution characteristics of air pollutants according to elemental carbon, crystalline silica, and stable isotope ratio - (대구 안심연료단지 환경오염물질 노출 평가(III) - 원소 탄소, 결정형 실리카 및 안정동위원소비를 이용한 오염원 기여율 및 분포특성 -)

  • Jung, Jong-Hyeon;Phee, Young-Gyu;Shon, Byung-Hyun;Bae, Hye-Jeong;Yang, Won-Ho;Kim, Ji-Young;Kim, Geun-Bae;Choi, Jong-Woo;Park, Sung-Jun;Lee, Kwan;Lim, Hyun-Sul
    • 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.

Isotopic dietary history of Neolithic people from Janghang site at Gadeok Island, Busan (부산 가덕도 장항 유적 출토 인골의 안정동위원소 분석을 통해 본 신석기시대의 식생활 양상)

  • Shin, Ji Young;Kang, Da Young;Kim, Sang Hyun;Jung, Eui Do
    • 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.

Recent Technological Advances in Optical Instruments and Future Applications for in Situ Stable Isotope Analysis of CH4 in the Surface Ocean and Marine Atmosphere (표층해수 내 용존 메탄 탄소동위원소 실시간 측정을 위한 광학기기의 개발 및 활용 전망)

  • PARK, MI-KYUNG;PARK, SUNYOUNG
    • 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.

Preparation of Pure CO2 Standard Gas from Calcium Carbonate for Stable Isotope Analysis (탄산칼슘을 이용한 이산화탄소 안정동위원소 표준시료 제작에 대한 연구)

  • Park, Mi-Kyung;Park, Sunyoung;Kang, Dong-Jin;Li, Shanlan;Kim, Jae-Yeon;Jo, Chun Ok;Kim, Jooil;Kim, Kyung-Ryul
    • 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.

Calibration of δ13C values of CO2 gas with different concentrations in the analysis with Laser Absorption Spectrometry (레이저흡광분석기(Laser Absorption Spectrometry)를 이용한 CO2가스의 탄소안정동위원소비 보정식 산출)

  • Jeong, Taeyang;Woo, Nam C.;Shin, Woo-Jin;Bong, Yeon-Sik;Choi, Seunghyun;Kim, Youn-Tae
    • Economic and Environmental Geology
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    • v.50 no.6
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    • pp.537-544
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    • 2017
  • Stable carbon isotope ratio of carbon dioxide (${\delta}^{13}C_{CO2}$) is used as an important indicator in the researches for global climate change and carbon capture and sequestration technology. The ${\delta}^{13}C$ value has been usually analyzed with Isotope Ratio Mass Spectrometer (IRMS). Recently, the use of Laser Absorption Spectrometry (LAS) is increasing because of the cost efficiency and field applicability. The purpose of this study was to suggest practical procedures to prepare laboratory reference gases for ${\delta}^{13}C_{CO2}$ analysis using LAS. $CO_2$ gas was adjusted to have the concentrations within the analytical range. Then, the concentration of $CO_2$ was assessed in a lab approved by the Korea Laboratory Accreditation Scheme and the ${\delta}^{13}C_{CO2}$ value was measured by IRMS. When the instrument ran over 12 hours, the ${\delta}^{13}C$ values were drifted up to ${\pm}10$‰ if the concentration of $CO_2$ was shifted up to 1.0% of relative standard deviation. Therefore, periodical investigation of analytical suitability and correction should be conducted. Because ${\delta}^{13}C_{CO2}$ showed the dependency on $CO_2$ concentration, we suggested the equation for calibrating the concentration effect. After calibration, ${\delta}^{13}C_{CO2}$ was well matched with the result of IRMS within ${\pm}0.52$‰.

Comparison of Solidification Pre-treatment Methods for the Determination of δ13C of Dissolved Organic Carbon: Alkaline Persulfate Oxidation-Carbonate Precipitation vs. Freeze Drying (용존유기탄소의 δ13C : 분석시 고형화 전처리 방법 비교 알칼린 과황산칼륨산화 탄산침전과 동결건조)

  • Jeon, Byeong-Jun;Park, Hyun-Jin;Choi, Woo-Jung;Park, Yong-Se;Lee, Sang-Mo;Yoon, Kwang-Sik
    • Korean Journal of Environmental Agriculture
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    • v.36 no.2
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    • pp.113-118
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    • 2017
  • BACKGROUND: The carbon (C) isotope ratio (${\delta}^{13}C$) of dissolved organic C (DOC) is an indicator of water pollution source. In this study, the potential use of two pre-treatments for the ${\delta}^{13}C$ analysis, alkaline persulfate oxidation coupled with carbonate precipitation (precipitation) and freeze drying (drying), were compared to suggest a more feasible pre-treatment method. METHODS AND RESULTS: Two reference materials with different ${\delta}^{13}C$ values were used for the experiments; chemical grade glucose ($-12.0{\pm}0.02$‰) and pig manure compost extract ($-23.3{\pm}0.04$‰). In the precipitation method, the measured ${\delta}^{13}C$ values were consistently lower than the theoretically calculated values as dissolved $CO_2$ could not be removed due to the alkaline property of the reagents and the dissolution of air $CO_2$ into the alkaline solution. The drying method also resulted in more negative ${\delta}^{13}C$ than the calculated ${\delta}^{13}C$; however, the difference was systematic ($3.9{\pm}0.3$‰) and there was a strong correlation (${\delta}^{13}C_{calculated}=0.87{\times}{\delta}^{13}C_{measured}-0.624$, $r^2=0.98$) between the calculated and measured ${\delta}^{13}C$. Calibration of ${\delta}^{13}C$ using the relationship between the calculated and the measured ${\delta}^{13}C$ values produced reliable and accurate ${\delta}^{13}C$ values. CONCLUSION: Our results suggest that the drying method is more accurate pre-treatment method to minimize the influence of air $CO_2$ compared to the precipitation method for the determination of ${\delta}^{13}C$ of DOC.