• Title/Summary/Keyword: 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.

DETERMINATION OF BURNUP AND PU/U RATIO OF PWR SPENT FUELS BY GAMMA-RAY SPECTROMETRY

  • Park, Kwang-June;Ju, June-Sik;Kim, Jung-Suk;Shin, Hee-Sung;Chun, Yong-Bum;Kim, Ho-Dong
    • Nuclear Engineering and Technology
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    • v.41 no.10
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    • pp.1307-1314
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    • 2009
  • The isotope ratio of $^{134}Cs/^{137}Cs$ in a spent PWR fuel sample was obtained with a newly developed gamma/neutron combined measuring system at KAERI. Burnup and Pu/U ratio of the spent fuel sample were determined by using the measured isotope ratio and the burnup-isotope ratio correlation equations calculated from the ORIGEN-ARP computer code. The results were compared and evaluated with the chemically determined burnup and Pu/U ratio. As a result of the comparative evaluation, the nondestructively determined burnup and Pu/U ratio values showed a good agreement with the chemically obtained results to within a 4.5% and 0.8% difference, respectively.

Experimental validation of a nuclear forensics methodology for source reactor-type discrimination of chemically separated plutonium

  • Osborn, Jeremy M.;Glennon, Kevin J.;Kitcher, Evans D.;Burns, Jonathan D.;Folden, Charles M. III;Chirayath, Sunil S.
    • Nuclear Engineering and Technology
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    • v.51 no.2
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    • pp.384-393
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    • 2019
  • An experimental validation of a nuclear forensics methodology for the source reactor-type discrimination of separated weapons-useable plutonium is presented. The methodology uses measured values of intra-element isotope ratios of plutonium and fission product contaminants. MCNP radiation transport codes were used for various reactor core modeling and fuel burnup simulations. A reactor-dependent library of intra-element isotope ratio values as a function of burnup and time since irradiation was created from the simulation results. The experimental validation of the methodology was achieved by performing two low-burnup experimental irradiations, resulting in distinct fuel samples containing sub-milligram quantities of weapons-useable plutonium. The irradiated samples were subjected to gamma and mass spectrometry to measure several intra-element isotope ratios. For each reactor in the library, a maximum likelihood calculation was utilized to compare the measured and simulated intra-element isotope ratio values, producing a likelihood value which is proportional to the probability of observing the measured ratio values, given a particular reactor in the library. The measured intra-element isotope ratio values of both irradiated samples and its comparison with the simulation predictions using maximum likelihood analyses are presented. The analyses validate the nuclear forensics methodology developed.

Determination of Li by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

  • Park, Chang J.;Chung, Bag S.
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.427-434
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    • 1995
  • Inductively coupled plasma mass spectrometry combined with the isotope dilution method is used for the determination of lithium. The isotope dilution method is based on the addition of a known amount of enriched isotope (spike) to a sample. The analyte concentration is obtained by measuring the altered isotope ratio. The spike solution is calibrated through so called reverse isotope dilution with a primary standard. The spike calibration is an important step to minimize error in the determined concentration. It has been found essential to add spike to a sample and the primary standard so that the two isotope ratios should be as dose as possible. Since lithium is neither corrosive nor toxic, lithium is used as a chemical tracer in the nuclear power plants to measure feedwater flow rate. 99.9% $^7Li$ was injected into a feedwater line of an experimental system and sample were taken downstream to be spiked with 95% $^6Li$ for the isotope dilution measurements. Effects of uncertainties in the spike enrichment and isotope ratio measurement error at various spike-to-sample ratios are presented together with the flow rate measurement results in comparison with a vortex flow meter.

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Chemical Compositions and Lead Isotope Ratios of Some Glass Beads from Seokga-tap, Gyeongju

  • Kang, Hyung-Tae;Yun, Eun-Young
    • Conservation and Restoration of Cultural Heritage
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    • v.1 no.1
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    • pp.3-8
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    • 2012
  • Chemical compositions and lead isotope ratios for four glass bead samples of Seokga-tap were analyzed and the results were organized. Among 4 glass beads found in the Seokga-tap, 3 pieces were lead glass. Manufacturing method was to firstly grind pebbles finely and mix lead ore to be melt at $740{\sim}760^{\circ}C$. The mixed ratio of silica and lead was 3:7. Moreover, The evaluation on the lead isotope ratio indicated that two lead glass pieces used lead ore from northern Korea. One piece has the direction of southern Korea lead ore, but it requires a further review. One glass bead of Seokga-tap was brown and it was potash lead glass ($K_2O-PbO-SiO_2$) System. The mixed ratio was approximately 50:10:40 for silica, natural saltpeter, and lead, respectively. Lead isotope ratio data fell within the lead ore from northern China. Therefore, it was concluded that potash lead glass found in the Seokga-tap was produced in northern area of China at the end of $10^{th}$ century and transferred to the Seokga-tap.

Verification of Graphite Isotope Ratio Method Combined With Polynomial Regression for the Estimation of Cumulative Plutonium Production in a Graphite-Moderated Reactor

  • Kim, Kyeongwon;Han, Jinseok;Lee, Hyun Chul;Jang, Junkyung;Lee, Deokjung
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.19 no.4
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    • pp.447-457
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    • 2021
  • Graphite Isotope Ratio Method (GIRM) can be used to estimate plutonium production in a graphite-moderated reactor. This study presents verification results for the GIRM combined with a 3-D polynomial regression function to estimate cumulative plutonium production in a graphite-moderated reactor. Using the 3-D Monte-Carlo method, verification was done by comparing the cumulative plutonium production with the GIRM. The GIRM can estimate plutonium production for specific sampling points using a function that is based on an isotope ratio of impurity elements. In this study, the 10B/11B isotope ratio was chosen and calculated for sampling points. Then, 3-D polynomial regression was used to derive a function that represents a whole core cumulative plutonium production map. To verify the accuracy of the GIRM with polynomial regression, the reference value of plutonium production was calculated using a Monte-Carlo code, MCS, up to 4250 days of depletion. Moreover, the amount of plutonium produced in certain axial layers and fuel pins at 1250, 2250, and 3250 days of depletion was obtained and used for additional verification. As a result, the difference in the total cumulative plutonium production based on the MCS and GIRM results was found below 3.1% with regard to the root mean square (RMS) error.

Feasibility Study of Isotope Ratio Analysis of Individual Uranium-Plutonium Mixed Oxide Particles with SIMS and ICP-MS

  • Esaka, Fumitaka;Magara, Masaaki;Suzuki, Daisuke;Miyamoto, Yutaka;Lee, Chi-Gyu;Kimura, Takaumi
    • Mass Spectrometry Letters
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    • v.2 no.4
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    • pp.80-83
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    • 2011
  • Isotope ratio analysis of nuclear materials in individual particles is of great importance for nuclear safeguards. Although secondary ion mass spectrometry (SIMS) and thermal ionization mass spectrometry (TIMS) are utilized for the analysis of individual uranium particles, few studies were conducted for the analysis of individual uranium-plutonium mixed oxide particles. In this study, we applied SIMS and inductively coupled plasma mass spectrometry (ICP-MS) to the isotope ratio analysis of individual U-Pu mixed oxide particles. In the analysis of individual U-Pu particles prepared from mixed solution of uranium and plutonium standard reference materials, accurate $^{235}U/^{238}U$, $^{240}Pu/^{239}Pu$ and $^{242}Pu/^{239}Pu$ isotope ratios were obtained with both methods. However, accurate analysis of $^{241}Pu/^{239}Pu$ isotope ratio was impossible, due to the interference of the $^{241}Am$ peak to the $^{241}Pu$ peak. In addition, it was indicated that the interference of the $^{238}UH$ peak to the $^{239}Pu$ peak has a possibility to prevent accurate analysis of plutonium isotope ratios. These problems would be avoided by a combination of ICP-MS and chemical separation of uranium, plutonium and americium in individual U-Pu particles.

Classification of Obsidian Artifacts found in the Korean Peninsula using Sr isotope ratio (Sr 동위원소비를 이용한 한반도 흑요석의 분류 연구)

  • Cho Nam-Chul;Kang Hyung-Tae;Chung Gwang-Ryong
    • 한국문화재보존과학회:학술대회논문집
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    • 2005.11a
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    • pp.268-271
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    • 2005
  • Sixty-four obsidian artifacts found in the Korean Peninsula have been characterised by a study of their minor elements and Sr isotope ratio. The artifacts are from the following locations: Yondaedo Island; Yokjido Island; Sangnodaedo Island, Tongyeong, Gyeongnam; Dongsamdong, Busan; Songdo Island, Yeosu, Jeonnam; Suyanggae, Danyang, Chungbuk; Sangmuyongri, Yanggu, Gangwondo; Paektusan Mountain; Kyushu region, Japan. The study of minor elements and Sr isotope ratio recognised three distinct major groups. This result suggests that there are no correlations among the three groups whose provenances are different. But as a result of classification using Sr isotope ratio, obsidian artifacts found in the southern part of the Korean Peninsula classified two groups within C group. This research will furnish scientific datum to be able to mutual comparison of obsidians excavated from other site.

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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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