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論文

Heterogeneous aggregation of humic acids studied by small-angle neutron and X-ray scattering

斉藤 拓巳*; 元川 竜平; 大窪 貴洋*; 三浦 大輔*; 熊田 高之

Environmental Science & Technology, 57(26), p.9802 - 9810, 2023/07

 被引用回数:0 パーセンタイル:0(Engineering, Environmental)

Aggregation of humic acids (HAs) were studied by small-angle neutron and X-ray scattering techniques. The combination of these techniques enables us to examine aggregation structures of heterogeneous HA particles. Two HAs with distinctive compositions were examined; a commercial HA (PAHA) and a HA extracted from deep sedimentary groundwater (HHA). While macroscopic coagulation tests showed that these HAs were stable in solutions except for HHA at pH $$<$$ 6, small-angle neutron scattering (SANS) and X-ray scattering (SAXS) revealed that they formed aggregates with the sizes exceeding sub-micrometer length scale. The SAXS curves of PAHA remarkably varied with pD, whereas the SANS curves did not. With the help of theoretical fittings, it was revealed that PAHA aggregates consisted of two domains: poorly hydrated cores and well-hydrated proton-rich shells. The cores are (dis)aggregated with pD inside the aggregates of the shell. The SANS and SAXS curves of HHA resemble each other, and their intensities at low q increased with a decrease of pD, indicating the formation of homogeneous aggregates. This study revealed that distinctive aggregation behaviors exist in humic substances with heterogeneous structures like PAHA, which is invaluable for their roles in the fate of contaminants or nutrients in aqueous environments.

論文

Structural approach to understanding the solubility of metal hydroxides

小林 大志*; 中嶋 翔梧*; 元川 竜平; 松村 大樹; 斉藤 拓巳*; 佐々木 隆之*

Langmuir, 35(24), p.7995 - 8006, 2019/06

 被引用回数:5 パーセンタイル:22.5(Chemistry, Multidisciplinary)

We report the hierarchical structure of zirconium hydroxide after aging at different temperatures to elucidate the factors governing zirconium solubility in aqueous solutions. Zirconium hydroxide solid phases after aging at 25, 40, 60, and 90$$^{circ}$$C under acidic to alkaline conditions were investigated using extended X-ray absorption fine structure (EXAFS) and wide- and small-angle X-ray scattering (WAXS and SAXS) techniques to reveal the bulk and surface structures of the solid phases from the nanoscale to submicroscale. After aging at 25 $$^{circ}$$C, the fundamental building unit of the solid phase was a zirconium hydroxide tetramer. The tetramers formed primary particles approximately 3 nm in size, which in turn formed aggregates hundreds of nanometers in size. This hierarchical structure was found to be stable up to 60 $$^{circ}$$C under acidic and neutral conditions and up to 40 $$^{circ}$$C under alkaline conditions. After aging at 90 $$^{circ}$$C under acidic conditions and at 60 and 90 $$^{circ}$$C under alkaline conditions, the WAXS and EXAFS measurements suggested the crystallization of the solid phase. The transformation of the solid-phase structure by temperature was discussed in relation to the solubility product to understand the solubility-limiting solid phase. The solubility of zirconium hydroxide after aging at different temperatures was governed not only by the size of the primary particles, but also by their surface configuration.

報告書

セルオートマトン法による亀裂ミクロ構造を考慮した流体物質移動解析(先行基礎工学研究に関する平成16年度共同研究報告書)

西山 哲*; 上原 真一*; 矢野 隆夫*; 斉藤 竜平*; 内田 雅大; 澤田 淳; 武部 篤治

JNC TY8400 2005-007, 70 Pages, 2005/03

JNC-TY8400-2005-007.pdf:2.24MB

本研究では,岩盤不連続面のせん断時における透水特性を把握するために,せん断透水同時試験装置の開発を行い,人工供試体を用いてせん断透水試験を行った。せん断時の垂直方向の拘束形式としては垂直応力一定試験と垂直剛性一定試験を採用しており,基本的なパラメータである垂直応力&#61555;&#61558;,垂直剛性Kv,不連続面表面形状および動水勾配Iなどが透水特性に与える影響について考察した。また,開発したLGA解析コードを用いて,開口幅をパラメータとした平行平板中の流体解析を実施した。そして,その流体解析結果から,開口幅,動水勾配と流量の関係について検討を行い,LGA法の適用性を確認した。

口頭

On forming "giant clusters" in an acidic solution of Ce(IV) nitrates

青柳 登; 元川 竜平; 斉藤 拓巳*; 奥村 雅彦; 池田 篤史

no journal, , 

We aimed at finding out a structural order and interaction between intra/inter clustering molecules composed of tetravalent cerium ions and others at high concentration: e.g. ranging from 50.0 mM to 1.0 M. Surprisingly, we confirmed that the "giant cluster" with a diameter of ca. 25.4 nm was formed after examining X-ray small-angle scattering patterns in detail. Plus, this diameter enlarges as time evolves. Moreover, we demonstrate detailed analysis as well as model construction for theoretical calculation and verification on the formation and characteristics, whether or not agglomeration of primary clusters, of giant clusters.

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