Evaluating sulfur-impurity removal and modern carbon contamination in different preparation methods for radiocarbon dating of soil samples by accelerator mass spectrometry

Koarashi, Jun; Takeuchi, Erina; Kokubu, Yoko; Atarashi-Andoh, Mariko

Radiocarbon, 67(2), p.307 - 317, 2025/04

https://doi.org/10.1017/RDC.2024.137

Radiocarbon (C) dating of soil samples by accelerator mass spectrometry has been proven useful for studying carbon (C) cycling in terrestrial ecosystems. There are, however, two main difficulties in sample preparation for this application: contamination of samples with modern C and inhibition of graphite formation due to sulfur (S)-containing impurities. Here we evaluated these effects from three different sample preparation methods, by conducting C measurements of C-dead sample and S-rich soil samples. The preparation methods were all successful in graphite formation and C measurement for soil samples with an organic S content 6.9%. The different methods showed different percent Modern Carbon (pMC) values ranging from 0.19% to 0.64% for C-dead sample. However, the three methods had little influence on the determination of C age for samples at least younger than 12,000 yr BP. The methods examined in the present study can be used for C dating with sufficient accuracy in the application to C cycle studies.

Synthesis and characterisation of a new graphitic C-S compound obtained by high pressure decomposition of CS

Klotz, S.*; Baptiste, B.*; Hattori, Takanori; Feng, S. M.*; Jin, Ch.*; Bneut, K.*; Guigner, J. M.*; Estve, I.*

Carbon, 185, p.491 - 500, 2021/11

https://doi.org/10.1016/j.carbon.2021.09.048

Carbon disulphide (CS) is one of the simplest molecular systems made of double covalent bonds. Under high pressure, the molecular structure is expected to break up to form extended crystalline or polymeric solids. Here we show that by compression at 300 K to approximately 10 GPa using large-volume high pressure techniques, an instantaneous reaction leads to a mixture of pure sulphur and a well-defined compound with stoichiometry close to CS which can be recovered to ambient pressure. We present neutron and X-ray diffraction as well as Raman data which show that this material consists of sulphur bonded to sp graphite layers of nanometric dimensions. The compound is a semiconductor with a gap of 45 meV, as revealed by temperature dependent resistivity measurements, and annealing at temperatures above 200C allow to reduce its sulphur content up to CS. Its structural and electronic properties are fundamentally different to "Bridgman black" reported from previous high pressure experiments on CS.

A Suitable procedure for preparing of water samples used in radiocarbon intercomparison

Takahashi, Hiroshi*; Minami, Masayo*; Aramaki, Takafumi*; Handa, Hiroko*; Kokubu, Yoko; Ito, Shigeru*; Kumamoto, Yuichiro*

Radiocarbon, 61(6), p.1879 - 1887, 2019/12

https://doi.org/10.1017/RDC.2019.104

Water sample for interlaboratory comparison (here after "comparison water") must have inalterable C concentration during the comparison campaign and inter-batches homogeneity. In this study, the procedure for preparing of comparison water was discussed. We employed that comparison waters were artificially made by mixing chemical reagents, controlling C concentration and chemical composition. We could prepare six comparison waters, having 1, 14, 37, 56, 72 and 100 pMC, respectively. The stable carbon isotopic values and chemical compositions of some batches were measured to exanimate the inter- batches homogeneity. The C discrepancies among the batches were negligible for the inter-laboratory comparison. Finally, the results of trial comparison in Japan will be presented. Most of C results of CO extracted by six laboratories showed good agreements each other.

Preliminary test of the EA-AGE3 system for C measurement of CaCO samples and coral-based estimation of marine reservoir correction in the Ogasawara Islands, Northwestern Subtropical Pacific

Kokubu, Yoko; Mitsuguchi, Takehiro*; Watanabe, Takahiro; Yamada, Tsutomu*; Asami, Ryuji*; Iryu, Yasufumi*

Radiocarbon, 61(5), p.1593 - 1601, 2019/10

https://doi.org/10.1017/RDC.2019.69

We performed C measurements of two fossil and one modern corals using a combined system of an elemental analyzer and an automated graphitization equipment AGE3 (EA-AGE3 system) and JAEA-AMS-TONO. The C concentrations (pMC values) of mid-Holocene Okinawa corals obtained by our EA-AGE3 system appear to be slightly higher than those obtained by the conventional graphitization method using phosphoric acid. The pMC increase in our EA-AGE3 system may result in significant underestimation of C age especially for older samples (e.g., 10,000 BP); however, the pMC increase is negligible in C measurements of modern or recent samples. We applied the EA-AGE3 method to the pre- and post-bomb annual-band samples from the modern Ogasawara coral for C measurements. On the basis of the pre-bomb coral C data, we estimated marine reservoir correction (R) around Ogasawara Islands and its stability between 1900 and 1950 AD.

Electronic structure of Li@C; Photoelectron spectroscopy of the Li@C[PF] salt and STM of the single Li@C molecules on Cu(111)

Yamada, Yoichi*; Kuklin, A. V.*; Sato, Sho*; Esaka, Fumitaka; Sumi, Naoya*; Zhang, C.*; Sasaki, Masahiro*; Kwon, E.*; Kasama, Yasuhiko*; Avramov, P. V.*; et al.

Carbon, 133, p.23 - 30, 2018/07

https://doi.org/10.1016/j.carbon.2018.02.106

We report first STM observation of the Li ion endohedral C, which is of a new class of endohedral fullerenes, prepared by means of evaporation of high-purity Li@C[PF] salt in ultra-high vacuum. Prior to the STM measurements, the electronic structure of Li@C in the Li@C[PF] salt was also precisely determined. In the salt, it is shown that Li and PF have nearly single positive and negative charge, respectively, and the C cage is nearly neutral, suggesting that Li@C in the salt retains its original electronic state.

Comparison of C collected by precipitation and gas-strip methods for dating groundwater

Nakata, Kotaro*; Hasegawa, Takuma*; Iwatsuki, Teruki; Kato, Toshihiro

Radiocarbon, 58(3), p.491 - 503, 2016/09

AA2015-0781.pdf:0.96MB

https://doi.org/10.1017/RDC.2016.22

Dissolved inorganic carbon (DIC) for C analysis of groundwater is usually extracted by a gas-strip or precipitation method. In this study, the certainty of the two methods for C dating were confirmed. DIC and C concentrations obtained by the gas-strip method were close to the theoretically predicted C value. Conversely, the C value obtained by the precipitation method always showed higher values than the predicted values. The difference in C value between gas-strip and precipitation methods was assumed to arise owing to contamination of modern carbon used in the precipitation method. The applicability of the precipitation method for groundwater should be considered carefully according to the DIC, C concentration of groundwater and purpose of the study being conducted.

Thiophene adsorption on phosphorus- and nitrogen-doped graphites; Control of desulfurization properties of carbon materials by heteroatom doping

Shimoyama, Iwao; Baba, Yuji

Carbon, 98, p.115 - 125, 2016/03

https://doi.org/10.1016/j.carbon.2015.10.094

The amounts of adsorbed thiophene were compared among phosphorus- and nitrogen-doped graphite and graphite damaged by Ar irradiation to clarify the influence of heteroatom doping on the adsorptive desulfurization properties of -conjugated carbon materials. On the basis of thiophene coverages estimated from X-ray photoelectron spectroscopy, Phosphorus-doped graphite had an adsorption ability that was 10-20 times larger than that of Nitrogen-doped graphite, indicating that the adsorptive desulfurization property of carbon largely depends on dopant atoms. Polarization dependent analysis using near-edge X-ray absorption fine structure spectroscopy was used to distinguish the configurations at dopant sites, indicating that the curved structures of phosphorus sites exhibited approximately 10 times greater adsorption abilities when compared with the planar structures. Theoretical simulation using molecular orbital calculations indicated different dopant effects between phosphorus and nitrogen along with different thiophene adsorption behaviors between planar and curved structures. Finally, experimental thiophene desorption results obtained at different temperatures revealed an advantage of phosphorus doping for reactivation.

Current activities for research and development on accelerator-driven system in JAEA

Sugawara, Takanori; Nishihara, Kenji; Takei, Hayanori; Iwamoto, Hiroki; Oizumi, Akito; Sasa, Toshinobu; Tsujimoto, Kazufumi

Proceedings of 21st International Conference & Exhibition; Nuclear Fuel Cycle for a Low-Carbon Future (GLOBAL 2015) (USB Flash Drive), p.648 - 656, 2015/09

The JAEA has investigated an accelerator-driven system (ADS) to transmute minor actinides which will be partitioned from the high level waste. There are various inherent issues for the research and development on the ADS. This study introduces the current two activities to get a feasible and reliable ADS concept. For the feasibility, the beam window design is one of the most important issues. To mitigate the design condition of the beam window, namely to reduce the proton beam current, the subcritical core concepts with subcriticality adjustment mechanism were investigated. As the result, the proton beam current reduced from 20mA to 10mA by the installation of the control rods. For the reliability, the two accelerators concept was proposed and the beam trip frequency was estimated by the J-PARC LINAC data and Monte-Carlo method. Through these investigations, it was confirmed that the two accelerators concept was useful to realize reliable accelerator operation for the ADS.

Experimental study on boiling accident of high active liquid waste in reprocessing

Uchiyama, Gunzo; Tashiro, Shinsuke; Amano, Yuki; Abe, Hitoshi; Yamane, Yuichi; Yoshida, Kazuo; Ishikawa, Jun

Proceedings of 21st International Conference & Exhibition; Nuclear Fuel Cycle for a Low-Carbon Future (GLOBAL 2015) (USB Flash Drive), p.1056 - 1063, 2015/09

The experimental study for source term data of radioactive materials has been conducted at a boiling accident of high active liquid waste (HALW) in reprocessing plants. In the study, three kinds of tests have been conducted including a cold small scale test, a cold engineering scale test and a hot small scale test. The following results were obtained: Ruthenium and Technetium were released into the gas phase in the form of both mist and gas under the boiling accident conditions of a simulated HALW. Non-volatile fission products (FPs) such as Nd and Cs were released into the gas phase in the form of mist. The release ratios of non-volatile FPs from a vessel of the simulated HALW were about 10. The release ratios of actinide nuclides such as Am were almost the same as those of non-volatile FPs.

Concept for the single cycle process based on mutual separation by reverse extraction of actinides and fission products

Sasaki, Yuji; Tsubata, Yasuhiro; Shirasu, Noriko; Morita, Keisuke; Suzuki, Tomoya

Proceedings of 21st International Conference & Exhibition; Nuclear Fuel Cycle for a Low-Carbon Future (GLOBAL 2015) (USB Flash Drive), p.1653 - 1656, 2015/09

The concept for the new partitioning method of high-level radioactive waste (HLW) by single-cycle extraction process has been investigated. This process is based on extraction of actinides (An) and fission products (FP), and mutual separation by reverse extraction. Solo extractant and several stripping reagents will be utilized in this process. The extractant employed in this process is required to extract soft (platinum metals), hard acid metals(An), and oxonium anions (Mo, Tc) simultaneously. NTAamide is one of the candidate extractants. After extraction of An and FP by NTAamide(C8), the mutual separation among these metals by reverse extraction will be followed using the suitable water-miscible reagents. The extraction of An and FP, and the masking effect by some water-miscible reagents has been studied.