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長澤 真*; 清水 祐輔*; 山口 瑛子; 徳永 紘平; 向井 広樹*; 青柳 登; Mei, H.; 高橋 嘉夫*
Chemical Geology, 670, p.122431_1 - 122431_25, 2024/12
被引用回数：0 パーセンタイル：0.00(Geochemistry & Geophysics)Typical vertical profiles of ion-adsorption type rare earth element deposits (REE-IADs) discovered in the central Japan were studied by various speciation analyses including X-ray absorption fine structure (XAFS) and laser-induced fluorescence (LIF) spectroscopy combined with transmission electron microscope (TEM) and adsorption/desorption experiments. The results revealed that REE speciation, migration and enrichment in the weathered granite is largely controlled by soil pH which control the variable charges of kaolinite as the REE host phase. The distribution coefficient Kd, together with the soil pH, increases as the depth increase, resulting in (i) REE dissolution and migration in upper layers near the surface acidic environment where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree and (ii) REE accumulation in relatively high pH environment below the surface where hydroxyls of kaolinite basal surfaces and edges deprotonated to a larger degree to produce variable charges as adsorption sites for REEs. The increase of soil pH above 6 in deeper layers promotes inner-sphere complexation of REEs. The inner-sphere complexation inhibits the ion-exchange extraction of REEs, but the inner-sphere complexes can be still extracted by lowering the pH, which suggests the adsorption of inner- and outer-sphere complexes is reversible. This fact is important both from (i) understanding of vertical profile of REE with variation of pH and (ii) effective recovery of REE from weathered granite at all the depths in the enriched layer.
and Eu
onto coherent and melange-type pre-neogene sedimentary rocksHou, L.*; 戸田 賀奈子*; Mei, H.; 青柳 登; 斉藤 拓巳*
Journal of Nuclear Science and Technology, 61(11), p.1488 - 1498, 2024/11
被引用回数：1 パーセンタイル：68.64(Nuclear Science & Technology)Widely present in Japan's deep subterranean formations, pre-Neogene sedimentary rocks offer an option for high-level radioactive waste (HLW) deep geological disposal due to their favorable properties. However, their barrier properties necessitate further investigation. This research examines the characteristics of pre-Neogene sedimentary rocks, focusing on two rock types: the melange type with a distinct block-in-matrix structure and the sandstone-dominant coherent type. Their ability and mechanism to sorb Cs and Eu are assessed, and the differences between the two types are compared. The influence of inorganic carbon in groundwater and the role of clay minerals, such as illite, in the sorption of these metal ions, are highlighted. This investigation lays the groundwork for future studies on migration behaviors of radionuclides, essential for ensuring the long-term safety of HLW geological disposal.
杉浦 佑樹; 石寺 孝充; 青柳 登; Mei, H.; 斉藤 拓巳*; 舘 幸男
Applied Clay Science, 258, p.107476_1 - 107476_10, 2024/09
被引用回数：1 パーセンタイル：63.07(Chemistry, Physical)This study performed batch sorption experiments using Eu and Sm as chemical analogs of trivalent actinides to evaluate their sorption behavior onto illite in the presence of dissolved inorganic carbon (DIC). The results were analyzed using a thermodynamic sorption model (TSM), which predicted that Eu/Sm forms ternary-surface complexes with carbonate ions. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements were performed to gather information on the chemical forms of sorbed Eu on illite. Parallel factor analysis (PARAFAC) of the TRLFS data indicated the presence of two Eu chemical species. The pH dependence of the chemical species was consistent with that of the surface species predicted by TSM. The dominant chemical species in the presence of carbonate was inferred to be coordinating carbonate ions based on the fluorescence lifetime, supporting the validity of the TSM.
Mei, H.; 青柳 登; 斉藤 拓巳*; 田中 万也; 杉浦 佑樹; 舘 幸男
Applied Geochemistry, 162, p.105926_1 - 105926_8, 2024/02
被引用回数：2 パーセンタイル：77.71(Geochemistry & Geophysics)The sorption of U(VI) on illite at different pH and dissolved inorganic carbon (DIC) levels was investigated by using batch experiments, surface complexation modeling, and cryogenic time-resolved laser fluorescence spectroscopy (cryo-TRLFS) combined with parallel factor analysis (PARAFAC). The inhibiting effect of DIC on U(VI) sorption was revealed by the macroscopic batch experimental results. An updated 2-site protolysis non-electrostatic surface complexation and cation exchange model considering the formation of two uranyl-carbonate sorption complexes was able to reproduce the experimental results well. Based on the PARAFAC analysis on the cryo-TRLFS spectra, there was clear correspondence in the variation trend of the derived components with the sorption species from the modeling results, validating the formation of ternary uranyl-carbonate sorption species.
Liu, J.; 土津田 雄馬; 北垣 徹; 青柳 登; Mei, H.; 高野 公秀; 香西 直文
Journal of Nuclear Science and Technology, 60(8), p.1002 - 1012, 2023/08
被引用回数：1 パーセンタイル：30.19(Nuclear Science & Technology)This study aims to reveal the potential bacterial alteration of nuclear fuel debris. A melt simulant composed of U
ZrO
and Fe(0), and three powder simulants (UO, Fe(0), and their mixed powder) were prepared and exposed to Bacillus subtilis in a Fe-deficient medium under aerobic conditions. B. subtilis could not dissolve Zr from the melt simulant but enhanced the dissolution of U and Fe, although the change of the melt simulant was too small to evaluate. Experiments using powder simulants were performed to investigate the bacterial influence in detail. B. subtilis enhanced the dissolution of U from the UO powder and Fe from the Fe(0) powder, although the dissolution of U was low. Most aqueous U species were probably U(VI), while the U that remained as a solid phase was mostly U(IV). The Fe(0) powder was oxidized by this bacterium, transforming it into an aqueous and solid Fe species. The stable species consisted of amorphous nano-sized particles. A fraction of the dissolved Fe was adsorbed or precipitated onto the UO particles and remained undissolved. These results strongly suggest that bacteria can degrade nuclear fuel debris, although this study did not elucidate the mechanism of oxidative dissolution.
室田 健人*; 青柳 登; Mei, H.; 斉藤 拓巳*
Applied Geochemistry, 152, p.105620_1 - 105620_11, 2023/05
被引用回数：4 パーセンタイル：62.63(Geochemistry & Geophysics)The confinement in small spaces influences the complicated reaction involving water molecules under electrostatic potentials at the solid-liquid interface. It is unclear, in particular, how the hydration state of metal ions adsorbed on the surface changes as a function of the pore size. This study analyzed the adsorption states of europium aqua ions on mesoporous silicas with different pore distributions in comparison with nonporous silica using time-resolved laser-induced fluorescence spectroscopy. The parallel factor analysis was used to differentiate the contribution of different chemical species of Eu(III) to the fluorescence signal and determine the influence of the pore size on each chemical species. The results show that Eu(III) mainly form outer-sphere complexes with silica below pH 6, where Eu(III) adsorption is low. Within nano-sized pores, distortion of the hydration structure and a decrease in the hydration number were suggested in this pH range. As the concentration of the silicate ions derived from the dissolution of silica increases with increasing pH, Eu(III) form the silica/Eu(III) /silicate ternary surface complexes. Within nano-sized pores, the concentration of silicate ions decreases due to the overlap of the electric double layer, which inhibits the formation of the ternary surface complex. Furthermore, at high pH, Eu(III) multinuclear complexes formed only on the mesoporous silica surface. This adsorption behavior specific to nano-sized pores could not be concluded by macroscopic adsorption experiments alone because the amount of Eu adsorbed per unit surface area did not differ between the mesoporous and nonporous silicas. Consideration of the silicate complexes should be indispensable in future studies on the adsorption of lanthanide ions using mesoporous silica.
BaCo(PO
)Sheng, J.*; Wang, L.*; Candini, A.*; Jiang, W.*; Huang, L.*; Xi, B.*; Zhao, J.*; Ge, H.*; Zhao, N.*; Fu, Y.*; et al.
Proceedings of the National Academy of Sciences of the United States of America, 119(51), p.e2211193119_1 - e2211193119_9, 2022/12
被引用回数：24 パーセンタイル：89.85(Multidisciplinary Sciences)Although considerable progress has been made in the theoretical understanding of the low-dimensional frustrated quantum magnets, experimental realizations of a well-established scaling analysis are still scarce. This is particularly true for the two-dimensional antiferromagnetic triangular lattices. Owing to the small exchange strength, the newly discovered compound NaBaCo(PO) provides a rare opportunity for clarifying the quantum criticality in an ideal triangular lattice with quantum spin S=1/2. In addition to the establishment of the complete phase diagrams, the spin Hamiltonian with a negligible interplane interaction has been determined through the spin wave dispersion in the polarized state, which is consistent with the observation of a two-dimensional quantum critical point with the Bose-Einstein condensation of diluted free bosons.
Mei, H.; 青柳 登; 斉藤 拓巳*; 香西 直文; 杉浦 佑樹; 舘 幸男
Applied Geochemistry, 136, p.105178_1 - 105178_8, 2022/01
被引用回数：20 パーセンタイル：90.37(Geochemistry & Geophysics)Dissolved inorganic carbonate ions (DIC) present in groundwaters may affect both the aqueous and surface species of U(VI) due to its strong complexation ability with U(VI). However, it is still not clear how DIC affects U(VI) sorption on illite, which is one of the critical components in argillaceous rocks. In this study, the sorption of U(VI) on conditioned illite du Puy in presence of varying DIC concentrations (up to 250 mM DIC) as a function of pH was investigated by combining batch sorption experiments, surface complexation modeling, and the cryogenic time-resolved laser fluorescence spectroscopy (TRLFS). The distribution coefficients of U(VI) were sensitive to the DIC concentration, which decreased with an increase of DIC. There is no sorption of U(VI) under relatively high DIC concentrations (100 mM DIC). The U(VI) sorption behavior on illite was modeled by using the 2 Site Protolysis Non-Electrostatic Surface Complexation and Cation Exchange model. Two ternary surface complexation reactions with carbonate were needed to depict the experimental sorption data in addition to binary and ternary hydroxo surface complexation reactions employed for the description of U sorption to illite without carbonate. The cryogenic TRLFS revealed that U(VI) did sorb to illite in presence of high DIC concentration (up to 10 mM DIC). The spectra were unchanged with DIC at pH 8.5, suggesting the surface speciation of U(VI) remained the same. The decay curves were biexponential, which further indicated that at least two species were responsible for the sorption. Our finding will help to predict the transport and retention behaviors of U(VI) near radioactive waste repositories.
室田 健人*; 青柳 登; Mei, H.; 斉藤 拓巳*
no journal, ,
放射性廃棄物から溶出した放射性核種の地下環境中の動態においては、移行の過程での岩石や緩衝材内部の微小な空隙への吸着が重要な機構である。メソスケール(2
50nm)やナノスケール(2nm以下)の微小な空隙内での水の性質がより大きな空隙内でのそれと異なることが報告されているが、イオンの吸着がどのように異なるのかは明らかでない。そこで、微小空隙を有する岩石の模擬物質として、異なる径のメソ空隙を持つメソポーラスシリカに対しEu(III)を吸着させ、その吸着状態をTRLFSで分析した。得られたデータを多変量解析することで、空隙サイズによってEu(III)の吸着状態がどのように変化するのかについて調べた結果を報告する。
Mei, H.; 青柳 登; 斉藤 拓巳*; 香西 直文; 舘 幸男
no journal, ,
Carbonate ions in groundwater are believed to influence migration behaviors of radionuclides in the geological environment by formation of aqueous carbonate complexes. However, little is known about the possibility of sorption of the radionuclide-carbonate complexes on minerals. We investigate U(VI) sorption on an illite mineral as functions of pH and carbonate concentrations, by combining cryogenic time-resolved laser fluorescence spectroscopy and surface complexation modeling. We will present the macroscopic and microscopic results of the speciation of U(VI) in the presence of carbonate and discuss the modeling of the sorption data, reflecting the speciation data.
Mei, H.; 青柳 登; 斉藤 拓巳*; 杉浦 佑樹; 石寺 孝充; 田中 万也; 舘 幸男
no journal, ,
The sorption of U(VI) and trivalent lanthanides on illite at different pH and dissolved inorganic carbon (DIC) levels was investigated. The obvious inhibition effect of DIC on U(VI) and trivalent lanthanides sorption was revealed from the macroscopic batch experimental results. The formation of carbonate-containing sorption complexes was needed to be considered in the updated 2-site protolysis non-electrostatic surface complexation and cation exchange model to reproduce the experimental results. Based on the Parallel Factor Analysis analysis on the cryogenic time-resolved laser fluorescence spectroscopy spectra, the formation of ternary carbonate-containing sorption complexes was successfully identified. Identification of the sorption species adds more credibility to the predictive sorption model, which provides more confidence in the safety assessment of deep geological disposal.
Mei, H.; 青柳 登; 斉藤 拓巳*; 香西 直文; 杉浦 佑樹; 舘 幸男
no journal, ,
U(VI) sorption on illite in the presence of varying concentrations of carbonate ions was investigated by using the cryogenic TRLFS technique. The sorption species were differentiated by analyzing the fluorescent spectral shape and lifetime and using Parallel Factor Analysis.
杉浦 佑樹; 石寺 孝充; 青柳 登; Mei, H.; 斉藤 拓巳*; 舘 幸男
no journal, ,
The sorption behavior of trivalent lanthanides (Eu/Sm) onto illite in the presence of dissolved inorganic carbon (DIC) was investigated by batch sorption experiments. The results of the experiments were interpreted using a thermodynamic sorption model (TSM). The TSM predicted that Eu/Sm forms clay mineral-Eu/Sm-carbonate surface ternary complexes. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements were performed to obtain information on the chemical forms of Eu sorbed on illite. Parallel factor (PARAFAC) analysis of the TRLFS data indicated the presence of multiple chemical species. The pH dependence of the relative intensity of the chemical species derived from PARAFAC analysis was consistent with that of the surface species predicted by the TSM. The dominant chemical species in the presence of DIC was inferred to be coordinating carbonate ions based on the fluorescence lifetime. These results confirm the existence of surface ternary complex and the validity of the TSM.
