• Title/Summary/Keyword: isotope ratio.

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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.

Chemical Compositions of Glass Beads from Tombs of Hakso-ri Site, O'chang (오창 학소리유적 토광묘내 유리구슬의 화학적 특성 - 37호 및 40호 -)

  • Chung, Kwang Yong;Kang, Hyung Tae;Koh, Min Jeong;Kim, Hwa Jung
    • 보존과학연구
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    • s.32
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    • pp.113-121
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    • 2011
  • Four glass beads from Hakso-ri site, O'chang were analyzed for thirteen oxides with SEM/EDS and lead isotope ratios with TIMS respectively. These samples were classified to potash glass system($K_2O-CaO-SiO_2$) with HCLA(High CaO, Low $Al_2O_3$). However three samples with above 4% for lead could be classified to potash-lead ($K_2O-PbO-CaO-SiO_2$)glass system and it seemed that coloring agent for greenish blue was Cu. Lead isotope ratio data for four samples did not make a group but scattered to the space respectively. It needs more study for compositions and lead iosotope data of potash-lead glasses with regions and ages.

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Stable Carbon Isotope Signature of Dissolved Inorganic Carbon (DIC) in Two Streams with Contrasting Watershed Environments: A Potential Indicator for Assessing Stream Ecosystem Health

  • Kim, Chulgoo;Choi, Jong-Yun;Choi, Byungwoong;Lee, JunSeok;Jeon, Yonglak;Yi, Taewoo
    • Proceedings of the National Institute of Ecology of the Republic of Korea
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    • v.2 no.4
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    • pp.259-273
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    • 2021
  • We conducted a study to investigate the characteristics of the carbon cycle of two streams (located in Shig a Prefecture, Japan), having similar size, namely, the Adokawa stream (length: 52 km, area: 305 km2, watershed population: 8,000) and the Yasukawa stream (length: 62 km, area: 380 km2, watershed population: 120,000), but with different degree of human activity. Samples were collected from these two streams at 14 (Adokawa stream) and 23 (Yasukawa stream) stations in the flowing direction. The dissolved inorganic carbon (DIC) concentration and the stable carbon isotope ratio of DIC (δ13C-DIC) were measured in addition to the watershed features and the chemical variables of the stream water. The δ13C-DIC (-9.50 ± 2.54‰), DIC concentration (249 ± 76 µM), and electric conductivity (52 ± 13 µS/cm) in Adokawa stream showed small variations from upstream to downstream. However, the δ13C-DIC (-8.68 ± 2.3‰) upstream of Yasukawa stream was similar to that of Adokawa stream and decreased downstream (-12.13 ± 0.43‰). DIC concentration (upstream: 272 ± 89 µM, downstream: 690 ± 37 µM) and electric conductivity (upstream: 69 ± 17 µS/cm, downstream: 193 ± 37 µS/cm) were higher downstream than upstream of Yasukawa stream. The DIC concentration of Yasukawa stream was significantly correlated with watershed environmental variables, such as, watershed population density (r = 0.8581, p<0.0001, n = 23), and forest area percentage of the watershed (r = -0.9188, p<0.0001, n = 23). δ13C-DIC showed significant negative correlation with the DIC concentration (r = -0.7734, p<0.0001, n = 23), electric conductivity (r = -0.5396, p = 0.0079, n = 23), and watershed population density (r = -0.6836, p = 0.0003, n = 23). Our approach using a stable carbon isotope ratio suggests that DIC concentration and δ13C-DIC could be used as indicators for monitoring the health of stream ecosystems with different watershed characteristics.

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.

A Correction Method for the Peak Tailing Backgrounds for Accurate Isotope Ratio Measurements of Uranium in Ultra Trace Levels using Thermal Ionization Mass Spectrometry

  • Park, Jong-Ho;Choi, In-Hee;Park, Su-Jin;Lee, Myung-Ho;Song, Kyu-Seok
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4327-4331
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    • 2011
  • A new method in thermal ionization mass spectrometry (TIMS) was developed to correct peak tailing backgrounds in the isotope ratio measurements of uranium in ultra trace levels for higher accuracy. Two different uranium standard reference materials (U005 and U030) were used to construct databases of signal intensities at mass 234 u and mass 236 u, which correspond to the two uranium minor isotopes, and signal intensity of $^{238}U$. Correlations between peak tailing backgrounds and $^{238}U$ were obtained by least-squares regression on calculated backgrounds at mass 234 u and mass 236 u with respect to the signal intensity of $^{238}U$ followed by separation of the peak tails of the two major isotopes of uranium ($^{235}U$ and $^{238}U$), which enables us to obtain a master equation for peak tailing background correction on all kinds of samples. Verification of the correction method was carried out using U010 and IRMM-040a.

Spatial and Temporal Variations of δ13C and C/N in Suspended Particulate Organic Matter in the Gangneung Namdae Stream, Korea (강릉 남대천 부유입자유기물의 탄소안정동위원소 비와 C/N 비의 시·공간 변동)

  • Kwak, Jung Hyun;Park, Hyun Je
    • Journal of Environmental Science International
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    • v.29 no.5
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    • pp.531-539
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    • 2020
  • To understand the composition, quantity, and quality of Suspended Particulate Organic Matter (SPOM) in the Gangneung Namdae Stream, Korea, we examined spatiotemporal variations in water temperature, salinity, chlorophlly a (Chl a), Particulate Organic Carbon (POC) and nitrogen (PON), and carbon stable isotope (δ13C) of SPOM at six stations in June (pre-monsoon), July (monsoon), and September (post-monsoon) 2017. With increasing precipitation, the average POC and C/N values increased significantly in July than in June. In September, the values decreased with decreasing precipitation. The δ13C values showed irregular spatiotemporal fluctuations among the stations and periods, thereby suggesting a greater contribution of autochthonous organic matter to the pool of SPOM than that of allochthonous organic matter derived from upstream. In addition, the large and irregular changes in POC, C/N ratio, C:Chl a, and δ13C compared to that of PON were observed for all periods among the stations, indicating a serial discontinuity of the stream. Our results suggest that the Gangneung Namdae Stream is significantly influenced by the increase in freshwater discharge caused by heavy rainfalls during the summer monsoon and post-monsoon periods.

Characteristice Study of Ancient Northeast Asian Lead Glass and Green Glaze Based on Analysis Results (분석자료를 기초한 고대 납유리와 녹유의 특성 연구)

  • Lee, Jihee;Kim, Hyunjeong
    • Conservation Science in Museum
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    • v.24
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    • pp.99-116
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    • 2020
  • This study examines the results of analyses of the lead isotope ratio and chemical composition of lead glass and green glaze from ancient Northeast Asia in order to suggest their production sites and reveal further characteristics. The comparison of the lead isotope ratio of lead glass and green glaze from two Baekje remains in Iksan-the Wanggung-ri Site and Mireuksa Temple Site-suggests that they were produced to the west of the South Gyeonggi Massif (Zone 4) using lead extracted from the same area. With a few exceptions, it has proved difficult to identify the production sites of most of the green-glazed roof tiles from Unified Silla-period Buddhist temples across Northeast Asia. The major component of the lead glass from Baekje, Silla, China, and Japan during the seventh century is PbO, SiO2, Al2O3, CuO, and Fe2O3, with a ratio of PbO and SiO2 of 70 and 30 wt.%, respectively. The green-glazed roof tiles excavated from a temple from the Unified Silla period have a high proportion of lead, ranging from 64 to 90 wt.%. Green-glazed lozenge tiles excavated from the Sacheonwangsa Temple site in Gyeongju were shown to contain PbO, SiO2, Al2O3, and CuO, a similar composition with lead glass. An experiment was conducted to reproduce a glaze according to the production method mentioned in the Zō hotokesho sakumotsu-chō (Buddhist statue workshop crop book) in the Shosoin Repository. In this experiment, an identical ratio of PbO was observed for Japanese green-glazed ceramics from the eighth to eleventh century as that found in Chinese lead-glazed ceramics excavated from kilns operated from the seventh to tenth century in Henan. This indicates that production methods for lead glass and glaze were shared across Northeast Asia.

Isotope Measurement of Uranium at Ultratrace Levels Using Multicollector Inductively Coupled Plasma Mass Spectrometry

  • Oh, Seong-Y.;Lee, Seon-A.;Park, Jong-Ho;Lee, Myung-Ho;Song, Kyu-Seok
    • Mass Spectrometry Letters
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    • v.3 no.2
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    • pp.54-57
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    • 2012
  • Mass spectrometric analysis was carried out using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) for the precise and accurate determination of the isotope ratios of ultratrace levels of uranium dissolved in 3% $HNO_3$. We used the certified reference material (CRM) 112-A at a trace level of 100 pg/mL for the uranium isotopic measurement. Multiple collectors were utilized for the simultaneous measurement of uranium isotopes to reduce the signal uncertainty due to variations in the ion beam intensity over time. Mass bias correction was applied to the measured U isotopes to improve the precision and accuracy. Furthermore, elemental standard solution with certified values of platinum, iridium, gold, and thallium dissolved in 3% $HNO_3$ were analyzed to investigate the formation rates of the polyatomic ions of $Ir^{40}$ $Ar^+$, $Pt^{40}$ $Ar^+$, $Tl^{40}$ $Ar^+$, $Au^{40}$ $Ar^+$ for the concentration range of 50-400 pg/mL. Those polyatomic ions have mass-to-charge ratios in the 230-245 m/z region that it would contribute to the increase of background intensity of uranium, thorium, plutonium, and americium isotopes. The effect of the polyatomic ion interference on uranium isotope measurement has been estimated.

Determination of Mercury in Fly Ash by Using Flow Injection Cold Vapor Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

  • Suh, Jung-Ki;Min, Hyung-Sik;Kamruzzaman, Mohammad;Lee, Sang-Hak
    • Mass Spectrometry Letters
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    • v.3 no.2
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    • pp.58-61
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    • 2012
  • A method based on flow injection-isotope dilution-cold vapor-inductively coupled plasma mass spectrometry (FI-IDCV-ICP/MS) has been applied to determine trace level of mercury in fly ash. $^{200}Hg$ isotopic spike was added to 0.25 g of BCR176R fly ash and then decomposed by microwave digestion procedure with acid mixture A (8 mL $HNO_3$ + 2 mL HCl + 2 mL HF) and acid mixture B (8 mL $HNO_3$ + 2 mL $HClO_4$ + 2 mL HF) for applying IDMS. Mercury cold vapor was generated by using reductant solution of 0.2% (w/w) $NaBH_4$ and 0.05% (w/w) NaOH. The measurements of n($^{200}Hg$)/n($^{202}Hg$) isotope ratio was made using a quadrupole ICP/MS system. The accuracy in this method was verified by the analysis of certified reference material (CRM) of fly ash (BCR 176R). The indicative value of Hg in BCR 176R fly ash was $1.60{\pm}0.23$ mg/kg (k = 2). The determined values of Hg in BCR 176R fly ash by the method of FI-CV-ID-ICP/MS described in this paper were $1.60{\pm}0.24$ mg/kg (k = 3.18) and the analysis results were in well agreement with the indicative value within the range of uncertainty.