• Title/Summary/Keyword: isotope fractionation

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Accurate Measurement of Isotope Amount Ratios of Lead in Bronze with Multicollector Inductively Coupled Plasma Mass Spectrometry

  • Lee, Kyoung-Seok;Kim, Jin-Il;Yim, Yong-Hyeon;Hwang, Euijin;Kim, Tae Kyu
    • Mass Spectrometry Letters
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    • v.4 no.4
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    • pp.87-90
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    • 2013
  • Isotope amount ratios of lead in a bronze sample have been successfully determined using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Matrix separation conditions were tested and optimized using ion exchange chromatography with anion-exchange resin, AG1-X8, and sequential elution of the 0.5 M HBr and 7 M $HNO_3$ to separate lead from very high contents of copper and tin in bronze matrix. Mercury was also removed efficiently in the optimized separation condition. The instrumental isotope fractionation of lead in the MC-ICP-MS measurement was corrected by the external standard sample bracketing method using an external standard, NIST SRM 981 lead common isotope ratio standard followed by correction of procedure blank to obtain reliable isotope ratios of lead. The isotope ratios, $^{206}Pb/^{204}Pb$, $^{207}Pb/^{204}Pb$, $^{208}Pb/^{204}Pb$, and $^{208}Pb/^{206}Pb$, of lead were determined as $18.0802{\pm}0.0114$, $15.5799{\pm}0.0099$, $38.0853{\pm}0.0241$, and $2.1065{\pm}0.0004$, respectively, and the determined isotope ratios showed good agreement with the reference values of an international comparison for the same sample within the stated uncertainties

Equilibrium Fractionation of Clumped Isotopes in H2O Molecule: Insights from Quantum Chemical Calculations (양자화학 계산을 이용한 H2O 분자의 Clumped 동위원소 분배특성 분석)

  • Sehyeong Roh;Sung Keun Lee
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.4
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    • pp.355-363
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    • 2023
  • In this study, we explore the nature of clumped isotopes of H2O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (16O, 17O, and 18O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H2O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT18O), 1.16 times (HT17O), and 0.703 times (HD17O) relative to HD18O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H2O including 17O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H2O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

Validation and Applications of Gas Chromatography-Combustion/isotope Ratio Mass Spectrometric Method to Control Misuse of Androgens in Human

  • Lee, Kang-Mi;Kim, Ho-Jun;Jeong, Eun-Sook;Yoo, Hye-Hyun;Kwon, Oh-Seung;Jin, Chang-Bae;Kim, Dong-Hyun;Lee, Jae-Ick
    • Mass Spectrometry Letters
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    • v.2 no.2
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    • pp.33-36
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    • 2011
  • The misuse of anabolic androgenic steroids is of particular concern in sports and society. Thus, it is of great importance to discriminate endogenous steroids such as testosterone or testosterone prohormones from their chemically identical synthetic copies. In this study, gas chromatography-combustion/isotope ratio mass spectrometric (GC-C/IRMS) method has been developed and validated for discriminating the origin of anabolic androgenic steroids. The method involves the solid-phase extraction, enzymatic hydrolysis with ${\beta}$-glucuronidase, HPLC-fractionation for the cleanup and analysis by GC-C/IRMS. The difference(${\Delta}^{13}C$) of urinary ${\delta}^{13}C$ values between synthetic analogues and endogenous reference compounds (ERC) by GC-C/IRMS was used to elucidate the origin of steroids, and intra- and inter-day precision, specificity and isotope fractionation were evaluated. The present GC-C/IRMS method combined with HPLC cleanup was accurate and reproducible enough to be successfully applied to the test of urine sample from suspected anabolic steroid abusers.

Ginseng authenticity testing by measuring carbon, nitrogen, and sulfur stable isotope compositions that differ based on cultivation land and organic fertilizer type

  • Chung, Ill-Min;Lee, Taek-Jun;Oh, Yong-Taek;Ghimire, Bimal Kumar;Jang, In-Bae;Kim, Seung-Hyun
    • Journal of Ginseng Research
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    • v.41 no.2
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    • pp.195-200
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    • 2017
  • Background: The natural ratios of carbon (C), nitrogen (N), and sulfur (S) stable isotopes can be varied in some specific living organisms owing to various isotopic fractionation processes in nature. Therefore, the analysis of C, N, and S stable isotope ratios in ginseng can provide a feasible method for determining ginseng authenticity depending on the cultivation land and type of fertilizer. Methods: C, N, and S stable isotope composition in 6-yr-old ginseng roots (Jagyeongjong variety) was measured by isotope ratio mass spectrometry. Results: The type of cultivation land and organic fertilizers affected the C, N, and S stable isotope ratio in ginseng (p < 0.05). The ${\delta}^{15}N_{AIR}$ and ${\delta}^{34}S_{VCDT}$ values in ginseng roots more significantly discriminated the cultivation land and type of organic fertilizers in ginseng cultivation than the ${\delta}^{13}C_{VPDB}$ value. The combination of ${\delta}^{13}C_{VPDB}$, ${\delta}^{15}N_{AIR}$, or ${\delta}^{34}S_{VCDT}$ in ginseng, except the combination ${\delta}^{13}C_{VPDB}-^{34}S_{VCDT}$, showed a better discrimination depending on soil type or fertilizer type. Conclusion: This case study provides preliminary results about the variation of C, N, and S isotope composition in ginseng according to the cultivation soil type and organic fertilizer type. Hence, our findings are potentially applicable to evaluate ginseng authenticity depending on cultivation conditions.

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.

THE ORIGINAL ENVIRONMENT OF THE SOLAR SYSTEM INFERRED FROM THE OXYGEN ISOTOPE ANOMALIES

  • Lee, Jeong-Eun;Bergin, Edwin A.;Lyons, James R.
    • Journal of The Korean Astronomical Society
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    • v.40 no.4
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    • pp.107-111
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    • 2007
  • The original environment of the solar system can be inferred by studying the oxygen isotope ratios in the Sun as well as in primitive meteorites and comets. The oxygen isotopic fractionation measured in primitive meteorites is mass-independent, which can be explained by the isotopic-selective photodissociation of CO. The isotopic-selective photodissociation model in a collapsing cloud by Lee et al. (2007) imply the birth of the Sun in a stellar cluster with an enhanced radiation field, which is consistent with the inferred presence of $^{60}Fe$.

A Study on the Quantitative Recovery of Dissolved Inorganic Carbonates in Ground Water for Radiocarbon Measurement (방사성탄소 측정을 위한 지하수 중에 용존된 무기탄소 화합물의 정량적 회수 연구)

  • Chun, Sang-Ki;Woo, Hyung-Joo;Cho, Soo-Young;Kim, Nak-Bae;Lee, Jong-Dae
    • Analytical Science and Technology
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    • v.12 no.4
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    • pp.284-289
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    • 1999
  • Dissolved inorganic carbonates in ground water were quantitatively recovered by using gas evolution method. Gas evolution method was found to be less time-consuming, less susceptible to the contamination fromatmospheric $CO_2$ and little affected by the sulfate ions in comparison to the direct precipitation method. Extraction efficiency of nearly 99% could be achieved by gas evolution method in two hours using recirculated gas at a sweeping rate of 4 liter per minute. Samples for carbon isotope fractionation study were collected in three fractions with collection times. The evolution time for the first fraction was one hours, and then second and third fractions were collected at intervals of 30 minutes, respectively. A small portion of each fraction was analyzed to evaluate ${\delta}^{13}C$ values, which were measured to be -7.9‰, -3.0‰ and +0,4‰ for the each fraction. The result clearly indicated that gas evolution method generates isotopically lighter carbon at the beginning of the purging process and heavier isotopes at the end. However, this isotope fractionation effect could be neglected by the almost complete recovery of carbonates.

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Monitoring and Analytical Techniques for the Discharged Radiocarbon from Nuclear Facility (핵시설로부터 발생되는 방사성탄소 분석기술 및 감시)

  • Chun, Sang-Ki;Kim, Nak-Bae;Kim, Kun-Han;Choi, Su-Young;Park, Chan-Jo;Lee, Joung-Dae;Shin, Jang-Sik
    • Analytical Science and Technology
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    • v.13 no.6
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    • pp.693-698
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    • 2000
  • The object of this series of experiments was aimed for the systematic and long-term radioactivity monitoring through indirect search of C-14 concentration level changes in the natural conditions around the operating nuclear facilities. The result of environmental radioactivity level through tree-ring analysis is increased after operating nuclear facilities and such a level can be proved to relate power generation closely. The measured result of ${\delta}^{13}C$ through the treatment of cellulose can be showed the level -30‰. This figure is very different from one which is measured the -17‰ of air sample by passive air sampling and -8‰ of air sample by active air sampling. And these differences can be assumed as isotope fractionation by photosynthesis, but the problem is more study as needed.

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Geochemical and S isotopic studies of pollutant evolution in groundwater after acid in situ leaching in a uranium mine area in Xinjiang

  • Zhenzhong Liu;Kaixuan Tan;Chunguang Li;Yongmei Li;Chong Zhang;Jing Song;Longcheng Liu
    • Nuclear Engineering and Technology
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    • v.55 no.4
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    • pp.1476-1484
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    • 2023
  • Laboratory experiments and point monitoring of reservoir sediments have proven that stable sulfate reduction (SSR) can lower the concentrations of toxic metals and sulfate in acidic groundwater for a long time. Here, we hypothesize that SSR occurred during in situ leaching after uranium mining, which can impact the fate of acid groundwater in an entire region. To test this, we applied a sulfur isotope fractionation method to analyze the mechanism for natural attenuation of contaminated groundwater produced by acid in situ leaching of uranium (Xinjiang, China). The results showed that δ34S increased over time after the cessation of uranium mining, and natural attenuation caused considerable, area-scale immobilization of sulfur corresponding to retention levels of 5.3%-48.3% while simultaneously decreasing the concentration of uranium. Isotopic evidence for SSR in the area, together with evidence for changes of pollutant concentrations, suggest that area-scale SSR is most likely also important at other acid mining sites for uranium, where retention of acid groundwater may be strengthened through natural attenuation. To recapitulate, the sulfur isotope fractionation method constitutes a relatively accurate tool for quantification of spatiotemporal trends for groundwater during migration and transformation resulting from acid in situ leaching of uranium in northern China.

Evaluation of Organic Matter Sources of Phytoplankton in Paldang Reservoir using Stable Isotope Analysis (팔당호 내 식물플랑크톤 안정동위원소 분석을 통한 유기물 기원 평가)

  • Kim, Jongmin;Kim, Bokyong;Kim, Minseob;Shin, Kisik
    • Journal of Korean Society on Water Environment
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    • v.31 no.2
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    • pp.159-165
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    • 2015
  • The organic matter sources of phytoplankton and related environmental factors influencing algal bloom in Paldang reservoir were studied using nitrogen and carbon isotope ratio(${\delta}^{15}N$, ${\delta}^{13}C$). Phytoplankton samples for stable isotope analysis were collected from four points in reservoir using a plankton net. Physicochemical water quality, algal taxa and hydrological data were collected from published monitoring material. Phytoplankton samples were analyzed by IRMS. CN ratio of each sample was very similar to that of phytoplankton from literature cited. ${\delta}^{15}N$ of each sample was decreased during July. Mixing and dilution of nitrogen sources due to increment of influx by concentrated rainfall were considered as the main reason for the decline of ${\delta}^{15}N$. Based on analyzed ${\delta}^{15}N$ value of each sample, nitrogen source of Bughan river sample was presumed to come from soil. The nitrogen sources of Namhan river and Kyeongan stream samples seemed to be sewage or animal waste. Low ${\delta}^{15}N$ value in August (2012) seemed to be influenced by isotope fractionation due to the blooming of nitrogen-fixation blue-green algae (Anabaena spp.). Variation in ${\delta}^{15}N$ values particularly by blue-green algal bloom was considered the important factor for estimating the organic matter sources of phytoplankton.