稻田土壤溶解性有机质组成及其与Cd2+络合过程研究
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X53

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国家自然科学基金项目(42167006)和江西省现代农业产业技术体系建设专项项目(JXARS-12-环境控制)资助


Research of Paddy Soil Dissolved Organic Matter Composition and Its Binding Process with Cd2+
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Supported by the National Natural Science Foundation of China (No. 42167006), and the Earmarked Fund for Jiangxi Agriculture Research System, China (No. JXARS-12- Environmental Control)

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    摘要:

    镉(Cd)是我国稻田土壤超标率最高的重金属污染物。土壤的溶解性有机质(DOM)影响Cd的生物有效性和迁移性。稻田是我国重要的粮食产地,同时稻田种养作为重要的生态农业模式,稻田环境改建和养殖等环节会改变DOM,但稻田以及稻田种养过程中土壤DOM与Cd2+的络合过程尚未清晰。基于紫外可见-吸收光谱、三维荧光光谱和同步荧光光谱,结合平行因子分析和二维相关分析、修正型Stern-Volmer 络合反应模型等方法,以稻虾种养(RS)和水稻单作(CK)两种模式作为试验对象,对稻田土壤DOM与Cd2+的络合过程进行研究。结果显示,RS与CK土壤DOM组分相似,包括一个色氨酸物质组分(C1)和三个类腐殖质组分(C2、C3、C4),相比CK,RS的C2和C4比例低,C3比例较高,C1差异不显著;紫外吸光度CK较RS高,吸收峰位于200~230 nm;同步荧光和二维相关分析表明,两种稻田系统土壤DOM荧光强度随Cd2+增加而发生变化,但不同模式土壤DOM与Cd2+的络合顺序不同,RS土壤DOM与Cd2+发生络合作用的顺序依次为腐殖质(310 nm)、色氨酸、腐殖质(375 nm),而CK为色氨酸、腐殖质(375 nm)、腐殖质(310 nm);络合反应模型表明稻田土壤DOM中色氨酸组分C1和富里酸组分C4与Cd2+络合后发生了显著的荧光猝灭,且C1和C4的络合常数lgK值表现为RS>CK。上述结果表明,RS与CK的土壤DOM均以腐殖质为主,但二者组成比例不同,DOM中存在较多芳香结构,这影响了腐殖质DOM与Cd2+的络合稳定性,种养同时也增强了色氨酸和富里酸DOM与Cd2+的络合能力。本研究结果可为稻田土壤Cd的污染机理研究与污染防治提供科学参考。

    Abstract:

    【Objective】 Cadmium (Cd) is the heavy metal pollutant with the highest over-limit rate in paddy soil in China. The bioavailability and mobility of Cd are affected by dissolved organic matter (DOM) in the soil. Paddy fields are important food production areas in China. As an important ecological agriculture mode in the rice industry, integrated planting and breeding of rice fields is of great significance to rural revitalization. The modification of paddy field environments and fishing can change DOM, but the complexation process between soil DOM and Cd2+ in paddy soil and during integrated planting and breeding of rice field process has not been clearly understood. 【Method】 In this study, the complexation process between DOM and Cd2+ in rice-shrimp cultivation (RS) and rice monoculture (CK) systems was investigated using a comprehensive array of analytical techniques, including ultraviolet-visible absorption spectrum (UV-Vis), 3D fluorescence spectroscopy, synchronous fluorescence spectroscopy, parallel factor analysis (PARAFAC), 2D correlation analysis (2D-COS), and the modified Stern-Volmer binding reaction model. Herein, RS was taken as an example of integrated planting and breeding of rice fields.【Result】 The PARAFAC analysis showed that soil DOM components of RS and CK were similar, including 1 tryptophan (C1) and 3 humus components (C2, C3, C4). Compared with CK, the proportions of C2 and C4 in soil DOM of RS were lower, while C3 was higher, and C1 was not significantly different. The UV-vis spectrum showed that DOM absorbance in CK was higher than in RS, with the absorption peak mainly located at 200-230 nm. With the increase of Cd2+, the change of UV-vis spectrum and UV254 was significantly different between RS and CK. Synchronous fluorescence spectra and 2D-COS analysis showed that paddy soil DOM fluorescence intensity changed with the increase of Cd2+, three absorption peaks were found by synchronous fluorescence spectra in DOM of paddy soil, which were the peak of tryptophan at 270 nm and the humus peak at 310 nm and 370 nm, respectively. The binding order between soil DOM and Cd2+ in RS was humus (310 nm), tryptophan, and humus (375 nm), respectively. However, in CK, the binding order was tryptophan, humus (375 nm), humus (310 nm). In the Stern-Volmer binding reaction model, the fluorescence intensity of C1 and C4 decreased with the increase of Cd2+, but the fluorescence intensity of C2 and C3 was unstable, which showed that the complexation of humus components C2 and C3 with Cd2+ had instability. This also led to the failure of fitting C2 and C3 in the model. The complexation constants lgK of C1 and C4 in the soil DOM of RS were 4.25 and 5.03, which were higher than in CK.【Conclusion】 The soil DOM in RS and CK mainly consisted of humus and the material composition ratio of soil DOM in RS was different. The complex process of DOM and Cd2+ in paddy soil belonged to static quenching and the aromatic structure affected the stability of DOM and Cd2+ complexation. Also, RS influenced the binding ability of tryptophan and fulvic acid DOM to Cd2+ whereas the instability of the complexation of humus with Cd2+ and the complexation of C4 with Cd2+ can enhance the bioavailability of Cd in soil. The results of this research can provide a scientific reference for the study of soil Cd pollution mechanism and pollution prevention in paddy fields.

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梁以豪,倪才英,黎衍亮,肖罗长,简敏菲.稻田土壤溶解性有机质组成及其与Cd2+络合过程研究[J].土壤学报,2025,62(1):153-164. DOI:10.11766/trxb202310180426 LIANG Yihao, NI Caiying, LI Yanliang, XIAO Luochang, JIAN Minfei. Research of Paddy Soil Dissolved Organic Matter Composition and Its Binding Process with Cd2+[J]. Acta Pedologica Sinica,2025,62(1):153-164.

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  • 收稿日期:2023-10-18
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