• Title/Summary/Keyword: Absolute isotope ratio

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Estimation of Mass Discrimination Factor for a Wide Range of m/z by Argon Artificial Isotope Mixtures and NF3 Gas

  • Min, Deullae;Lee, Jin Bok;Lee, Christopher;Lee, Dong Soo;Kim, Jin Seog
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2403-2409
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    • 2014
  • Absolute isotope ratio is a critical constituent in determination of atomic weight. To measure the absolute isotope ratio using a mass spectrometer, mass discrimination factor, $f_{MD}$, is needed to convert measured isotope ratio to real isotope ratio of gas molecules. If the $f_{MD}$ could be predicted, absolute isotope ratio of a chemical species would be measureable in absence of its enriched isotope pure materials or isotope references. This work employed gravimetrically prepared isotope mixtures of argon (Ar) to obtain $f_{MD}$ at m/z of 40 in the magnetic sector type gas mass spectrometer (gas/MS). Besides, we compare the nitrogen isotope ratio of nitrogen trifluoride ($NF_3$) with that of nitrogen molecule ($N_2$) decomposed from the same $NF_3$ thermally in order to identify the difference of $f_{MD}$ values in extensive m/z region from 28 to 71. Our result shows that $f_{MD}$ at m/z 40 was $-0.044%{\pm}0.017%$ (k = 1) from measurement of Ar artificial isotope mixtures. The $f_{MD}$ difference in the range of m/z from 28 to 71 is observed $-0.12%{\pm}0.14%$ from $NF_3$ and $N_2$. From combination of this work and reported $f_{MD}$ values by another team, IRMM, if $f_{MD}$ of $-0.16%{\pm}0.14%$ is applied to isotope ratio measurement from $N_2$ to $SF_6$, we can determine absolute isotope ratio within relative uncertainty of 0.2 %.

Development of chemical ionization method in a GC-TOF mass spectrometer for accurate mass and isotope ratio measurement (Accurate mass 및 isotope ratio 측정을 위한 GC-TOF 질량분석기에서의 화학적 이온화방법)

  • Chung, Joo-Hee;Na, Yun-Cheol;Hwang, Geum-Sook;Shin, Jeoung-Hwa;Ahn, Yun-Gyong
    • Analytical Science and Technology
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    • v.24 no.1
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    • pp.15-23
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    • 2011
  • An accurate mass and isotope ratio were determined using a gas chromatography/time of flight mass spectrometer in CI positive mode for the identification of unknown metabolites. High mass tune was used to improve the ion intensity of $[M+H]^+$. Chromatographic resolution and dynamic range enhancement were performed to obtain more reliable accurate masses and correct isotope abundance ratios. Average absolute errors of mass and isotope ratios for 24 reference metabolite -TMS (trimethylsilyl) derivatives were 6.8 ppm, 1.5% of (M+1/M ratio) and 1.7% of (M+2/M ratio), respectively. The correct formulas of twenty one compound were retrieved within top-2 hit from the heuristic algorithm for elemental composition using each accurate mass and isotope abundance ratio.

Variations in carbon and nitrogen stable isotopes and in heavy metal contents of mariculture kelp Undaria pinnatifida in Gijang, southeastern Korea

  • Shim, JeongHee;Kim, Jeong Bae;Hwang, Dong-Woon;Choi, Hee-Gu;Lee, Yoon
    • ALGAE
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    • v.32 no.4
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    • pp.349-357
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    • 2017
  • Korean mariculture Undaria pinnatifida was collected during the months of January, February, March, and December of 2010, as well as from January of 2011 to investigate the changes in the carbon and nitrogen stable isotope ratios (${\delta}^{13}C$ and ${\delta}^{15}N$) and heavy metal with respect to it growth and to identify the factors that influence such changes. The blades of U. pinnatifida showed ${\delta}^{13}C$ and ${\delta}^{15}N$ in the range (mean) of -13.11 to -19.42‰ (-16.93‰) and 2.99 to 7.57‰ (4.71‰), respectively. Among samples with the same grow-out period, those that weighed more tended to have higher ${\delta}^{13}C$ suggesting a close association between the carbon isotope ratio and growth rate of U. pinnatifida. Indeed, we found a very high positive linear correlation between the monthly average ${\delta}^{13}C$ and the absolute growth rate in weight ($r^2=0.89$). Nitrogen isotope ratio tended to be relatively lower when nitrogen content in the blade was higher, probably due to the strengthening of isotope fractionation stemming from plenty of nitrogen in the surrounding environment. In fact, a negative linear correlation was observed with the nitrate concentration in the nearby seawaters ($r^2=0.83$). Concentrations of Cu, Cd, Pb, Cr, Hg, and Fe in the blades showed a rapid decrease in their concentration per unit weight in the more mature U. pinnatifida. Specifically, compared to adult samples, Cu, Hg, and Pb were concentrated by 30, 55, and 73 folds, respectively, in the young blades. Therefore, U. pinnatifida tissue ${\delta}^{13}C$ is as an indirect indicator of its growth rate, while ${\delta}^{15}N$ values and heavy metal concentrations serve as tracers that reflect the environmental characteristics.

Investigation on the Stability of Uric Acid and its Isotope (1,3-15N2) in Ammonium Hydroxide for the Absolute Quantification of Uric Acid in Human Serum

  • Lee, Sun Young;Kim, Kwonseong;Oh, Han Bin;Hong, Jongki;Kang, Dukjin
    • 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.

A Suitability Study on the Indicator Isotopes for Graphite Isotope Ratio Method (GIRM) (흑연 동위원소 비율법의 지표 동위 원소 적합성 연구)

  • Han, Jinseok;Jang, Junkyung;Lee, Hyun Chul
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.18 no.1
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    • pp.83-90
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    • 2020
  • The Graphite Isotope Ratio Method (GIRM) can verify non-proliferation of nuclear weapon by estimating the total plutonium production in a graphite-moderated reactor. Using the reactor, plutonium is generated and accumulated through the 238U neutron capture reaction, and impurities in the graphite are converted to nuclides due to the nuclear reaction. Therefore, the amount of plutonium production and concentration of the impurities are correlated. However, the plutonium production cannot be predicted using only the absolute concentration of the impurities. It can only be predicted when the initial concentration of the impurities is obtained because the concentration, at a certain time, depends on it. Nevertheless, the ratios of the isotopes in an element are known regardless of the impurity of an element in the graphite moderator. Thus, the correlation between the isotope ratio and amount of plutonium produced helps predict plutonium production in a graphite-moderated reactor. Boron, Lithium, Chlorine, Titanium, and Uranium are known as indicator elements in the GIRM. To assess whether the correlation between the indicator isotope and amount of plutonium produced is independent of the initial concentration of the impurities, four different impurity compositions of graphite were used. 10B/11B, 36Cl/35Cl, 48Ti/49Ti, and 235U/238U had a consistent correlation with the cumulative plutonium production, regardless of the initial impurity concentration of the graphite, because these isotopes were not generated through the nuclear reaction of other elements. On the other hand, the correlation between 6Li/7Li and plutonium production depended on the initial concentration of the impurities in graphite. Although 7Li can be produced through the neutron capture reaction of 6Li, the (n, α) reaction of 10B was the major source of 7Li. Therefore, the initial concentration of 10B affected the production of 7Li, making Li unsuitable as an indicator element for the GIRM.

Environmental Change of High Moor in Mt. Dae-Am of Korean Peninsula (대암산 고층습원의 환경변천)

  • Yoshioka, Takahito;Kang, Sang-Joon
    • Korean Journal of Ecology and Environment
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    • v.38 no.1 s.110
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    • pp.45-53
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    • 2005
  • The environmental change of Yong-nup in Mt. Dae-Am, which is located at the northern part of Kangwon-Do, Korea, was assesed with peat sedimentary carbon and nitrogen isotope analysis. The surface layer of the peat (0 ${\sim}$ 5 cm) was 190 year BP, and the middle layers (30 ${\sim}$ 35 cm and 50 ${\sim}$ 55 cm) were 870 year BP and 1900 year BP, respectively. Bulk sedimentation rate was estimated to be about 0.4 mm $year^{-1}$ for 0 cm to 30 cm and 0.15 mm $year^{-1}$ for 35 cm to 50 cm. The $^{14}C$ age of the bottom sediment (75 ${\sim}$ 80 cm) collected and measured in this study was about 1900 year BP, although it was measured that the $^{14}C$ of the lowest bottom sediment in Yong-nup was 4105 ${\pm}$ 175 year BP (GX-23200). Since the $^{14}C$ ages for 50 ${\sim}$ 55 cm and 75 ${\sim}$ 80 cm layers were almost the same as 1890 ${\pm}$ 80 fear BP (NUTA 5364) and 1850 ${\pm}$ 90 year BP (NUTA 5462), respectively, we have estimated that the deep layers (55 ${\sim}$ 80 cm) in the high moor were the original forest soil. The low organic C and N contents in the deeper layers supported the inference. The sediment of 50 ${\sim}$ 55 cm layer contains much sandy material and showed very low organic content, suggesting the erosion (flooding) from the surrounding area. In this context, the Yong-nup, high moor, of Mt. Dae-Am, might have developed to the sampling site at about 1900 year BP. The ${\delta}^{13}C$ values of organic carbon and the ${\delta}^{15}N$ values of total nitrogen in the peat sediments fluctuated with the depths. The profile of ${\delta}^{13}C$ may indicate that the Yong-nup of Mt. Dae-Am have experienced the dry-wet and cool-warm period cycles during the development of the high moor. The ${\delta}^{15}N$ may indicate that the nitrogen cycling in the Yong-nup have changed from the closed (regeneration depending) system to the open (rain $NO_3\;^-$ and $N_2$ fixation depending) system during the development of the high moor.