热分析和红外光谱技术在表征土壤有机碳化学结构和热稳定中的应用

Application of Thermal Analysis and Infrared Spectroscopy to Characterize Chemical Structure and Thermal Stability of Soil Organic Carbon

  • 摘要:
    目的 探究应用热分析和红外光谱技术测定土壤有机碳化学结构和热稳定性的方法及可行性,为同时、快速、可靠表征有机碳组成及含量提供科学依据。
    方法 基于长期定位试验,设置7个施肥处理,分别为对照不施肥(CK)、单施氮磷钾化肥(NPK)、化肥氮的25%、50%、75%和100%由有机肥氮提供(分别为25%M、50%M、75%M和100%M)以及在NPK处理的基础上增加小麦和玉米秸秆还田(SNPK)。通过热分析和红外光谱技术测定不同施肥处理的土壤有机碳化学结构及稳定性特征。
    结果 结果发现,以空坩埚为对照、扣除测试背景值,使用10 mg的土壤样品,以10 K min−1的升温速率以及20 mL min−1的气体流量测定时,保证了样品的均匀性和代表性,同时保证了样品曲线的稳定性及样品的完全燃烧。基于此,进一步分析不同施肥处理下土壤的热分析曲线特征,发现样品失重主要分为盐和有机物的化学结合水和吸湿水损失(100℃ ~ 200℃)、有机质的脱氢和脱羧作用损失(200℃ ~ 400℃)、黏土矿物的脱羟基作用和极细颗粒的脱碳作用损失(400℃ ~ 650℃)、不同种类碳酸盐的挥发损失(650℃ ~ 900℃)4个阶段。由红外光谱特征峰发现,长期有机无机肥配施处理下土壤有机碳的化合物组分主要为羧酸、醇类、苯酚、多糖等物质。并且热分析第二阶段的失重量与有机碳化学官能团组分之间有显著相关性,尤其是与醇、酚类化合物和芳香族化合物呈极显著正相关关系(P < 0.001)。
    结论 热分析和红外分析技术均是半定量分析土壤有机碳质量和组分的有效方法,红外光谱特征峰和吸收峰面积也是表征有机碳化学官能团的有效手段。两者相互验证和结合可以更有效地分析不同有机肥替代化肥处理下土壤有机碳化学结构的变化。

     

    Abstract:
    Objective The aim was to explore the methods of using thermal analysis and infrared spectroscopy to determine the chemical structure and thermal stability of soil organic carbonation, so as to provide scientific basis for simultaneous, rapid and reliable characterization of organic carbon composition and content.
    Methods Based on the long-term positioning experiment, 7 fertilization treatments were set up. There were no control fertilization (CK), single application of NPK fertilizer (NPK), 25%, 50%, 75% and 100% of fertilizer nitrogen were provided by organic fertilizer nitrogen (25%M, 50%M, 75%M and 100%M, respectively), and the addition of wheat and corn straw returning to field (SNPK) on the basis of NPK treatment. The chemical structure and stability of soil organic carbonation under different fertilization treatments were determined by thermal analysis and infrared spectroscopy.
    Result The results showed that the uniformity and representativeness of the sample were ensured, and the stability of the sample curve and the complete combustion of the sample were ensured when the soil sample of 10 mg was measured at the heating rate of 10 K min−1 and the gas flow rate of 20 mL min−1, with the empty crucible as the control and the test background value deducted. Based on this, the thermal analysis curve characteristics of soil under different fertilization treatments were further analyzed. It is found that the weight loss of the sample was mainly divided into the loss of chemical binding water and hygrometric water of salt and organic matter (100℃-200℃), the loss of dehydrogenation and decarboxylation of organic matter (200℃-400℃), the loss of dehydroxylation of clay minerals and the loss of very fine particles (400℃ ~ 400℃). There were 4 stages of volatilization loss (650℃-900℃) of different kinds of carbonates. According to the characteristic peak of infrared spectrum, it was found that the compound components of soil organic carbon were mainly carboxylic acids, alcohols, phenols and polysaccharides under long-term application of organic and inorganic fertilizers. The weight loss in the second stage of thermal analysis was significantly correlated with organic carbonation functional group components, especially with alcohols, phenolic compounds and aromatic compounds (P < 0.001).
    Conclusion In summary, both thermal analysis and infrared analysis are effective methods for semi-quantitative analysis of soil organic carbon quality and composition, and infrared spectral characteristic peak and absorption peak area are also effective means for characterizing organic carbonation functional groups. The mutual verification and combination of the two can more effectively analyze the changes of soil organic carbonation chemical structure under different organic fertilizers instead of chemical fertilizers.

     

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