表面光谱-能谱技术解析氧化铁与硒代蛋氨酸的相互作用特征
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1.四川文理学院化学化工学院乡村低成本环境治理技术四川省高校重点实验室;2.硒资源研究与生物应用湖北省重点实验室(湖北民族大学);3.华中农业大学资源与环境学院

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国家自然科学基金项目(42467002)、四川文理学院高层次人才科研启动项目(2022GCC07Z)和乡村低成本环境治理技术四川省高校重点实验室开放基金项目(XCH2024ZB-04)资助


Revealing the Interaction Characteristics Between Selenomethionine and Iron Oxides over Surface Spectroscopy - Energy Spectrum Technique
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1.Key Laboratory of Low-cost Rural Environmental Treatment Technology at Sichuan University of Arts and Science, Education Department of Sichuan Province, Dazhou;2.Hubei Key Laboratory of Selenium Research and Biological Application(Hubei Minzu University), Enshi;3.College of Resources & Environment, Huazhong Agricultural University

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upported by the National Natural Science Foundation of China (No. 42467002), the Funding of Sichuan University of Arts and Science, China (No. 2022GCC07Z) and the Open Fund of Key Laboratory of Low-cost Rural Environmental Treatment Technology at Sichuan University of Arts and Science, Education Department of Sichuan Province (No. XCH2024ZB-04)

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    摘要:

    有机硒是土壤硒(Se)的重要存在形态,阐明有机硒与土壤氧化铁矿物之间的界面作用机制有助于深入理解硒元素在土壤环境中的迁移转化行为。通过测试水铁矿、针铁矿和赤铁矿吸附硒代蛋氨酸前后的X-射线光电子能谱(XPS)、X-射线吸收精细结构谱(XAFS)与衰减漫反射傅里叶红外光谱(DRIFTS-IR),分析了硒代蛋氨酸作用后的氧化铁表面物种、铁(Fe)元素配位结构以及吸附态硒代蛋氨酸的构型。结果表明:硒代蛋氨酸中的羧基以双齿配位垂直构型吸附于水铁矿表面;硒代蛋氨酸对针铁矿显示出明显的溶解效应,吸附态硒代蛋氨酸以卧式构型通过羧基与表面Fe原子发生单齿配位,并且存在Se原子与表面Fe的配位作用;硒代蛋氨酸对赤铁矿具有微弱的溶解性和最强的还原效应,氨基氮和Se原子均可通过表面配位作用吸附在赤铁矿表面。此外,三种氧化铁与硒代蛋氨酸相互作用时,硒代蛋氨酸存在完全矿化为亚硒酸根和不完全氧化的两种转化路径。

    Abstract:

    【Objective】Organic Se is an important component of total Se in soil, and selenomethionine exists as one of the most common species among the organic Se. Given that the interfacial interaction between iron oxides in soil and organic Se species remains elusive, this study provides an avenue for understanding the migration and transformation of Se coupling with Fe-cycling in soil. 【Method】 In this study, the interfacial interaction between selenomethionine and iron oxides, ferrihydrite, goethite, and hematite was investigated through the analysis of surface species, coordination structure of iron atom (Fe) and adsorption configuration over the X-ray photoelectron spectrum (XPS), X-ray absorption fine structure spectrum (XAFS), and attenuated diffuse reflection infrared spectrum (DRIFTS-IR). 【Result】The results revealed that the binding energy (B.E.) of N1s was decreased to 399.7 eV and it was maintained for the main Se species adsorbed on ferrihydrite. The coordination structure of first- and second-sphere for Fe atom of ferrihydrite before and after interacting with selenomethionine did not change, while there was an adsorbed carboxyl-species with bidentate coordination mode. This result suggested that selenomethionine could be adsorbed on ferrihydrite through the bidentate coordination mode with a vertical adsorption configuration over carboxyl on the surface of ferrihudrite. After interacting with selenomethionine, the B.E. of Fe for bulk FeO6 at the goethite sub-surface was reduced by 0.4 eV. Also, the distance of first-sphere and coordination number of outer spheres for Fe atom in goethite showed an obvious change, compared to that of the fresh goethite. It indicated that goethite had undergone an obvious dissolution accompanied by obvious reduction effect after interacting with selenomethionine. Moreover, the Se atom mainly existed as the oxidized species on goethite. There was a monodentate coordination mode for the adsorbed selenomethionine on goethite with a horizontal adsorption configuration. For hematite, the B.E. of Fe both at sub-surface and surface were reduced to 0.4 eV, while the coordination structure of Fe atom for the Fe-sphere did not change but shortened in the first-sphere. This phenomenon revealed a characteristic weak dissolution interaction and a strong reducibility for hematite interacted with selenomethionine. Owing to the reduction by selenomethionine, there was a strong surface-enhanced infrared absorption effect for the adsorbed selenomethionine. Besides, the amino N and Se atoms might directly participate in the chemical adsorption of selenomethionine on hematite. Among the three iron oxides, there was a similar oxidization pattern for Se during the interaction process and this observation can be summarized as: 1) the complete oxidization of selenomethionine into selenite and 2) the incomplete oxidization species of selenomethionine. 【Conclusion】The interaction characteristic and mechanism of selenomethionine with ferrihydrite, goethite, and hematite was carefully revealed through surface analysis. The results revealed a differential response for the surface structure of mineral and change of selenomethionine when it interacted with iron oxides with different surface structure and properties. These findings provide an important reference for understanding the migration and transformation of organic Se in soil under different Fe-cycling processes. It also provides guidance for the unitization of Se resource and remediation of Se pollution in Se-rich area.

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王锐,刘鑫,侯瑞晨,杨慧,杨顺评,谌雪乐,龙婷,向文军,魏世勇,谭文峰.表面光谱-能谱技术解析氧化铁与硒代蛋氨酸的相互作用特征[J].土壤学报,DOI:10.11766/trxb202503240131,[待发表]
WANG Rui, LIU Xin, HOU Ruicheng, YANG Hui, YANG Shunping, SHEN Xuele, LONG Ting, XIANG Wenjun, WEI Shiyong, TAN Wenfeng. Revealing the Interaction Characteristics Between Selenomethionine and Iron Oxides over Surface Spectroscopy - Energy Spectrum Technique[J]. Acta Pedologica Sinica, DOI:10.11766/trxb202503240131,[In Press]

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  • 收稿日期:2025-03-24
  • 最后修改日期:2025-07-03
  • 录用日期:2025-07-30
  • 在线发布日期: 2025-08-01
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