有机质去除对黄土纳米颗粒悬浮液稳定性的影响
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国家自然科学基金项目(41701261,41601236)和黄土高原土壤侵蚀与旱地农业国家重点实验室开放基金项目(A314021402-1909)资助


Effect of Organic Matter Removal on Stability of Suspension of Loess Nanoparticles
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Supported by the National Natural Science Foundation of China (Nos. 41701261 and 41601236) and the Open Fund of State Key Laboratory of Soil Erosion and Dryland Farming on the Loess Plateau (No. A314021402-1909)

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    摘要:

    土壤纳米颗粒是有机无机复合体,研究有机质对土壤纳米颗粒体系稳定性的影响具有重要意义。以塿土和褐土纳米颗粒以及去除有机质塿土和去除有机质褐土纳米颗粒为研究对象,分别测定颗粒的粒径分布、zeta电位、临界聚沉浓度(Critical coagulation concentration, CCC)等指标,利用德查金-朗道-维韦-奥弗比克(Derjauin-Landau-Verwey-Overbeek, DLVO)理论计算颗粒的哈默克(Hamaker)常数和相互作用能。结果表明:塿土和褐土纳米颗粒的平均直径分别为94.00 nm和88.20 nm,去有机质黄土纳米颗粒的平均直径则略高于100 nm;相较于黄土纳米颗粒,去有机质黄土纳米颗粒的zeta电位绝对值降低,颗粒间静电排斥势能降低;DLVO模型拟合得到塿土和褐土纳米颗粒在真空中的哈默克常数分别为6.86 × 10-20 J和9.73 × 10-20 J,去有机质处理后相应数值为3.14 × 10-20 J和3.40 × 10-20 J,后者范德华引力势能降低;去有机质黄土纳米颗粒间总势能高于黄土纳米颗粒,其CCC更大,稳定分散能力更强。土壤有机质含量越高,有机无机复合程度越高,颗粒越趋向于凝聚,这可能是有机质增强团聚体稳定性的原因之一。

    Abstract:

    【Objective】Soil nanoparticles are organic-mineral complexes. It is of great practical significance to study stability of the suspension of natural soil nanoparticles. However, so far little attention has been paid to effect of organic-mineral complexes on stability of soil nanoparticles, and let alone its mechanism. 【Method】 In this study soil nanoparticles were extracted, separately, from soil samples of Lou soil and cinnamon soil before and after soil organic matter was removed with the aid of the ultrasonic dispersion method and the Stokes’ law based high-speed centrifugation method for analysis of particle size distribution, zeta potential, critical coagulation concentration (CCC) in NaCl and CaCl2 solutions and characterized with the dynamic light scattering technique. Furthermore, Hamaker constants of and interaction energies between the soil nanoparticles were calcuated in line with the DLVO (Derjauin-Landau-Verwey-Overbeek) theory, mechanism of organic matter removal affecting stability of soil nanoparticle suspensions explored and role of organic-mineral complexation in stabilizing soil aggregates explained. 【Result】 Results show that the Lou and cinnamon soil nanoparticles were 94.00 nm and 88.20 nm, respectively, in average diameter and the OMR (organic matter removed) loess nanoparticles slightly higher than 100 nm; the obtained loess nanoparticles were all of the polydisperse system and quite approximate to each other in ploydispersity. The nanoparticles in the all the four types of loess soil samples carried negative charge on the surface and their zeta potential increased with rising pH of the solution in absolute value due to deprotonation of the functional groups on the surface of the organic matter. As the soils varied in clay mineral property, the nanoparticles in the cinnamon soil varied more sharply in surface zeta potential than those of the Lou soil; the cinnamon soil contained more variably-charged kaolinite, while the Lou soil contained more permanently-charged illite. The functional groups on the surface of organic matter, like alcoholic hydroxyl, phenolic hydroxyl and carboxyl, are the main sources of soil negative charges. Compared with the nanoparticles in the Lou and cinnamon soils, those in the OMR Lou and cinnamon were lower in absolute value of the zeta potential as they were lower in organic organic matter. The nanoparticles in the Lou and cinamon soils were 1.70 mmol·L-1 and 1.51 mmol·L-1, respectively, in CCC while those in the OMR Lou and cinnamon soils were 10.58 mmol·L-1 and 11.69 mmol·L-1; Obviously, removal of organic matter enhanced stability of the nanoparticle suspension. Based on DLVO-based simulation, the nanoparticles in the Lou and cinnamon soils in vacuum were 6.86 × 10-20 J and 9.73 × 10-20 J, in Hamaker constant and those in the OMR Lou and cinnamon soils were only 3.14 × 10-20 J and 3.40 × 10-20 J. Apparently, the Hamaker constants of the latters were lower than the formers and so were their van der Waals attractive potential energies. Lower absolute values of the zeta potentials of the nanoparticles in the OMR loess soils resulted in reduced electrostatic repulsive potential energies. Therefore, the removal of organic matter reduced both the van der Waals attractive potential energies and electrostatic repulsive potential energies of the nanoparticles in the loess soils. But the decrements in van der Waals attractive potential energy were higher in magnitue than those in electrostatic repulsive potential energy. Further calculations demonstrate that the nanoparticles in the OMR loess soils were higher in total potential energy than those in the Lou and cinnamon soils, which resulted in higher CCCs and higher dispersion stability of the suspensions. 【Conclusion】 The presence of organic matter affects stability of the nanoparticles in loess soils through adjusting both attractive and repulsive potential energies. The complexation of organic-mineral alters soil nanoparticle composition, which in turn determined their Hamaker constant. Removal of organic matter reduces Hamaker constants of the nanoparticles in loess, leading to low attractive potential energy between nanoparticles in OMR Lou and cinnamon soil. Therefore, it is concluded that organic-mineral complexation may enhance stability of soil aggregates through increasing Hamaker constant.

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王春丽,许晨阳,赵世伟,胡斐南,李琪瑞.有机质去除对黄土纳米颗粒悬浮液稳定性的影响[J].土壤学报,2020,57(1):119-129. DOI:10.11766/trxb201905300188 WANG Chunli, XU Chenyang, ZHAO Shiwei, HU Feinan, LI Qirui. Effect of Organic Matter Removal on Stability of Suspension of Loess Nanoparticles[J]. Acta Pedologica Sinica,2020,57(1):119-129.

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  • 收稿日期:2019-04-12
  • 最后修改日期:2019-07-16
  • 录用日期:2019-08-23
  • 在线发布日期: 2019-11-07
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