IRMS를 이용한 수소와 산소 안정동위원소의 정확도 및 정밀도 연구

황종연 ( Jong Yeon Hwang ),김보경 ( Bo Kyong Kim ),김민섭 ( Min Seob Kim ),이원석 ( Won Seok Lee ) 한국환경농학회 2013 한국환경농학회 학술대회집 Vol.2013 No.-

The isotope ratio mass spectrometer (IRMS) is an instrument that measures both of the elemental contents and isotope ratios of hydrogen, oxygen, carbon, nitrogen and sulfur in environmental samples at the same time. In this study, a recently introduced IRMS was used to analyze produced certified reference materials (CRMs), which helped establish analysis conditions of oxygen and hydrogen isotope ratios. It is important to ensure the reliability and present the accuracy and precision prior to applying environmental samples. In this study, three international standard materials such as VSMOW2, GISP and SLAP were employed. Among them, GISP was used for the calibration as it represents the intermediate hydrogen and oxygen isotope composition, while VSMOW2 and SLAP were applied to find the two end-points of δ D and δ18O values, respectively. In addition, the validation of accuracy and precision was performed with two CRMs indicating different isotope compositions. In analyzing δD and δ 18O values, the single analysis of each showed higher accuracy and precision than the simultaneous analysis of both during the calibration with GISP. The measured δ18O values of the two end-points were the same as the certified values of VSMOW (0 ‰) and SLAP (-55.5 ‰). However, the measured δD values, which were found-7.68 ‰ and-423.99 ‰, respectively, did not reach the certified values of VSMOW (0 ‰) and SLAP (-428 ‰). It is considered that the range (428 ‰) of hydrogen isotope ratios between the two international standards is quite wider than the range (55.5 ‰) of oxygen isotope ratios. Nonetheless, the gap between the two end-points was found to be narrowed from-0.57 ‰ of VSMOW to-420.87 ‰ of SLAP after calibration with VSMOW once H3 + factor correction was frequently performed every 1∼3 hours. The δ18O value of CRM certified as-19.64 ‰ fell within the certified value ±2σ in the range over around 39.9 nA, but the δD value of CRM certified as-152.02 ‰ was within the certified value ±4σ. In order to agree with the accepted values defined by VSMOW and SLAP, the measured δD values were switched over to the certified values through linear regression. As a result of normalization, the calculated δD values of CRM fell within the certified value ±2σ. In this study, the accuracy and precision of IRMS were assessed using CRMs, thereby establishing optimal analysis conditions for tracing environmental pollution sources.

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

( Fumitaka Esaka ),( Masaaki Magara ),( Daisuke Suzuki ),( Yutaka Miyamoto ),( Chi-gyu Lee ),( Takaumi Kimura ) 한국질량분석학회 2011 Mass spectrometry letters Vol.2 No.4

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 235U/238U, 240Pu/239Pu and 242Pu/239Pu isotope ratios were obtained with both methods. However, accurate analysis of 241Pu/239Pu isotope ratio was impossible, due to the interference of the 241Am peak to the 241Pu peak. In addition, it was indicated that the interference of the 238UH peak to the 239Pu 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.

Study on Strontium Isotope Abundance-Ratio Measurements by Using a 13-MeV Proton Beam

Cheol-Ki Jeong,Han Jang,Goung-Jin Lee 한국물리학회 2016 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.69 No.6

The Rb-Sr dating method is used in dating Paleozoic and Precambrian rocks. This method measures the 87Rb and the 87Sr concentrations by using thermal ionization mass spectrometry (TIMS) [J. Hefne et al., Inter. J. Phys. Sci. 3(1), 28 (2008)]. In addition, it calculates the initial 87Sr/86Sr ratio to increase the reliability of Rb-Sr dating. In this study, the 87Sr/86Sr ratio was measured by using a 13-MeV proton accelerator. Proton kinetic energies are in the range of tens of megaelectronvolts, and protons have large absorption cross-sections for (p, n) reactions with most substances. After absorbing a proton with such a high kinetic energy, an element is converted into a nuclide with its atomic number increased by one via nuclear transmutation. These nuclides usually have short half-lives and return to the original state through radioactive decay. When a strontium sample is irradiated with protons, nuclear transmutation occurs; thus, the strontium isotope present in the sample changes to a yttrium isotope, which is an activated radioisotope. Based on this, the 87Sr/86Sr ratio was calculated by analyzing the gamma-rays emitted by each yttrium isotope. The KIRAMS-13 cyclotron at the Cyclotron Center of Chosun University, where 13-MeV protons can be extracted, was utilized in our experiment. The 87Sr/86Sr isotope ratio was computed for samples irradiated with these protons, and the result was similar to the isotope ratio for the Standard Reference Material, i.e., 98.2 ± 3.4%. As part of the analysis, proton activation analyses were performed using 13-MeV protons, and the experimental results of this research suggest a possible approach for measuring the strontium-isotope abundance ratio of samples.

다중 검출 유도결합 플라즈마 질량분석기를 이용한 납 및 카드뮴안정동위원소비 분석의 질량 편향 보정방법 비교

김지영 ( Jee Young Kim ),김명진 ( Myung Jin Kim ),유은진 ( Eun Jin Yoo ),이강현 ( Kang Hyun Lee ),이경석 ( Kyoung Seok Lee ),이원석 ( Won Seok Lee ),최종우 ( Jong Woo Choi ),권오상 ( Oh Sang Kwan ) 한국환경분석학회 2014 환경분석과 독성보건 Vol.17 No.3

To obtain precise and accurate isotope ratios with a multi-collector ICP-MS, three methods such as interelementalinternal calibration, sample-standard bracketing (SSB), and log-log linear regression correction model were applied to isotope ratio measurement of lead (Pb) and cadmium (Cd) for the correction of instrumental mass discrimination. Certified reference materials including NIST SRM 981 (Pb), NIST SRM 3108(Cd), and BAM I012 (Cd) were used as reference materials for the isotope ratios of lead and cadmium to compare the corrected results obtained from the respective correction models. The accuracies of lead isotope ratio measurements were in the range of -0.002 (207/206Pb) to -0.035 (208/204Pb) % when the inter-elemental internal calibration applied. The same range of -0.002 (207/206Pb) to -0.035 (208/204Pb) % was also found with the SSB method. The log-log linear regression correction model, on the other hand, showed a different range of -2.160 (207/206Pb) to 0.219 (208/204Pb) %. The precisions of lead isotope ratios with these three correction methods ranged from 0.027 (206/204Pb) to 0.127 (208/204Pb), 0.025 (206/204Pb) to 0.124 (208/204Pb), and1.265 (207/204Pb) to 1.367 (207/206Pb), respectively. Therefore, both of the inter-elemental internal calibration and the SSB method were selected as good methods for mass bias correction of lead isotope ratios. Theε114/110Cd values obtained from the application of the three different correction models were -14.5±0.7 (Agas an internal standard), -13.0±2.1 (SSB), and -15.2±1.8 (log-log linear regression correction model), respectively. For ε114/110Cd values, the inter-elemental internal calibration showed the best precision among the three correction methods. Isobaric interferences with cadmium were also corrected when correction coefficients were applied to each isotope of cadmium. The difference of correction coefficients between the isotope ratios with natural abundances and the empirical ratios in the isobaric interferences reached up to 11%. The heavier isobaric interferences (106, 108, 110Pd vs. 105Pd) were underestimated in the application of the natural ratios, while the lighter isobaric interferences (112,114,116Sn vs. 118Sn and113In vs. 115In) were overestimated. In conclusion, the inter-elemental internal calibration and the SSB method can properly correct the isotope ratios of interest in the isotope ratio measurement using the MC-ICP-MS. Further research on the isotope ratio analysis of environmental samples should follow to improve precision and accuracy.

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 Korean Society for Mass Spectrometry 2011 Mass spectrometry letters Vol.2 No.4

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.

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

KWANG-JUNE PARK,주준식,JUNG-SUK KIM,HEE-SUNG SHIN,YONG-BUM CHUN,HO-DONG KIM 한국원자력학회 2009 Nuclear Engineering and Technology Vol.41 No.10

The isotope ratio of ¹³⁴Cs/¹³⁷Cs 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.

국립중앙박물관소장 금속유물의 납동위원소비 데이터베이스 구축(1)

강형태,안주영,허일권 국립중앙박물관 2007 박물관보존과학 Vol.8 No.-

국립중앙박물관 보존과학팀에서는 금속 유물의 보존처리 과정에서 얻은 청동 녹의 과학적 연구로서 납동위원소비 데이터를 구축하고 이로부터 청동기 원료의 산지와 관련된 연구를 수행하고자 한다. 청동 녹의 납동위원소비 분석을 위한 분석 장비는 기초과학지원연구소의 열이온화질량분석기(Thermal ionization mass spectromete ; TIMS)를 활용하였다. 본 연구의 일환으로 2007년에는 낙랑시대의 청동기 11점, 통일신라시대의 청동화형접시 등 6점, 고려시대 동종에서 4점의 청동 녹을 입수하였고 납동위원소비를 분석하였다. 기 분석한 한국, 중국 및 일본의 방연석 납동위원소비 데이터를 기초로 산지를 추정하였다. 앞으로 보존과학팀에서는 금속 유물의 보존처리를 수행하면서 얻을 수 있는 청동 녹을 최대한 수집하고 분석하여 이들 자료를 모아 유물의 종류별, 시기별, 지역별 산지연구를 위한 자료로 활용할 것이다. The Conservation Science Team of National Museum of Korea has established the data base of lead isotope ratio as the scientific research of bronze patina, which was acquired from conservation process of metal objects, and based on this result, it intends to conduct the research related to the production places of raw material for the bronze objects. As the equipment for analysis of lead isotope ratio of the bronze patina, the thermal ionization mass spectrometer (TIMS) was used. As part of the research, in 2007, the 11 samples of the bronze Patina from the objects, believed to belong to of Nangnang(Lelang), the 6 items of bronze patina from the flower-shaped bronze dishes, belong to Unified Silla period and 4 items from the Goryeo bronze bell were acquired and analyzed the lead isotope ratio. Based on the data of the lead isotope ratio from the galena of Korea, China and Japan, the provenance raw materials were estimated through the comparison of their lead isotope ratios. In the future, the Conservation Science Team of the National Museum of Korea will collect as much bronze patina as possible from the process of conservation treatment of metal objects, and analyze them in order to conduct the study of provenance with the type, period and the region of the objects.

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 Korean Nuclear Society 2009 Nuclear Engineering and Technology Vol.41 No.10

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.

First strontium isotope map of groundwater in South Korea: applications for identifying the geographical origin

신우진,류종식,김락현,민지숙 한국지질과학협의회 2021 Geosciences Journal Vol.25 No.2

In recent, strontium isotope ratios (87Sr/86Sr) have been commonly used as a geochemical tracer to investigate the geographic origin in various research fields, just comparing the data between samples. However, in forensic contexts it is much more important to predict and identify the origin for unknown samples rather than to compare the samples. Here, we collected about 500 groundwater samples from the National Groundwater Monitoring Wells in South Korea and measured their 87Sr/86Sr ratios representative of bioavailable 87Sr/86Sr ratios. The 87Sr/86Sr ratios of the samples ranged from 0.70540 to 0.86108, with a mean of 0.71890 ± 0.01509 (n = 504), reflecting the bedrock lithologies. Furthermore, the best interpolation methods were investigated using the measured 87Sr/86Sr ratios. The result indicates that the radical based function including spline with tension (RBF-ST) is the best interpolation method in terms of the prediction errors. Resulting strontium isotope map interpolated with RBF-ST mimics lithological distribution in South Korea. In order to evaluate the accuracy of the interpolation map, two animal bone samples were collected from two different provinces and measured their 87Sr/86Sr ratios. Although the estimated and measured 87Sr/86Sr ratios are not completely constant, the estimated 87Sr/86Sr ratios are within the range of those of groundwater samples near the site where the bone samples were collected, indicating that the interpolation map generated in this study can be used as a back-tracking technique to identify the geographical origin of unknown samples.

안정동위원소 비 측정을 위한 MC-ICP/MS 성능 평가 연구

최종우 ( Jong Woo Choi ),유은진 ( Eun Jin Yoo ),김종대 ( Jong Dae Kim ),이강현 ( Khang Hyun Lee ),이원석 ( Won Seok Lee ),한진석 ( Jin Seok Han ) 한국환경분석학회 2013 환경분석과 독성보건 Vol.16 No.1

This study was conducted to evaluate the performance of the MC-ICP/MS by using some standard metals to test five items such as sensitivity, mass resolving power, detector noise, mass stability and precision of isotope ratios. The sensitivities ranged from 148 to 578 Vppm-1 in the dry plasma system. The sensitivities were improved as much as 1.2∼2.5 times those of previous studies. The resolution (M/ΔM) at 10% peak height was as high as 8352 for 142Nd. The mass drift was 30 ppm of the peak range during the 30-minute measurement. Such high resolution and mass stability made it possible to separate purposed analytes from polyatomic interferents more effectively. The noise levels of faraday detectors (1.5∼2.7×10-5 V) and ion counting multipliers (0.01∼0.1 cps) were well below the performance standard. Analyzing the isotope ratios of Li, Sr, Nd, Pb and U standard solutions showed that all but Li isotope ratios were in good agreement with those reported in the previous studies. In conclusion, this study may build a new foundation for environmental research by suggesting the use of isotope ratios to trace heavy metal sources and estimate their contributions, which will overcome limitations in the existing methods of residual investigation and modeling.