溶解性有机物对土壤中农药残留与分布影响的光谱学研究

溶解性有机物(DOM)通过吸附、竞争吸附、增溶、加速降解等作用影响着农药在土壤环境中的行为，对土壤生态系统及地下水环境的污染与风险产生重要影响。目前多数研究集中在高浓度DOM对农药残留的短效影响。因此，对天然土壤中DOM及其组分对农药环境行为的研究具有重要的现实意义。该研究通过对具有较长农药使用年限的污染场地调查，利用三维激发-发射荧光光谱矩阵技术，结合荧光区域积分方法对天然土壤DOM进行定量化表征，在此基础上分析低浓度天然DOM对农药残留的长期影响。结果表明：(1)天然DOM组分对大多数有机氯农药在土壤中的环境行为影响较小，但对γ-HCH、p,p’-DDE等少数农药的影响较为显著。(2)不同DOM组分对不同种类的农药影响机制不同。其中，代表DOM组分中的酪氨酸含量的荧光区域积分与γ-HCH，p,p’-DDE之间均呈显著的负相关性(p<0.05)，代表DOM中微生物降解副产物组分的荧光区域积分与七氯以及代表DOM中胡敏酸大分子组分含量的荧光区域积分与环氧七氯之间均呈显著正相关性(p<0.05)，表明在土壤中长期作用过程中，DOM不同组分对不同种农药的影响不同。(3)土壤有机质的腐殖化程度对土壤中农药残留的影响较小。本研究首次利用三维荧光谱与区域积分技术研究了土壤中溶解性有机物不同组分对农药的环境行为的影响作用，对研究农药在土壤和地下水环境中的迁移转化机制提供了一种新的研究思路。

Using Three-Dimensional Fluorescence Spectrum Technology to Analyze the Effects of Natural Dissolved Organic Matter on the Pesticide Residues in the Soil

The behavior of pesticide in soil is influenced by dissolved organic matter (DOM) through competition adsorption, adsorption, solubilization, accelerated degradation, and so on. Thus DOM and its components play an important role in the environmental risk in the soil ecosystem and groundwater environment. Currently, most studies focused on the short-term effect of high concentration of DOM on the pesticide residues. However, soil DOM is mainly at low level. Therefore, there is of some practical significance to probe into the environmental behavior of soil pesticides under natural level of DOM. Thus a site investigation was conducted in the farmland with long-term application history of pesticide. By using the three dimensional excitation-emission fluorescence matrix (3D-EEM) technology, together with the fluorescence regional integration (FRI) quantitative method, the long-term effects of pesticide residues under low concentration of natural DOM were analyzed. Results showed that: (1) The long-term effects of the natural DOM components on the environment behavior of most soil organo-chlorine pesticides were not significant except for a few pesticides such as γ-HCH, p,p’-DDE, etc. (2) The influencing effects of DOM components on different type of pesticides were varied. Among which, the content of tyrosine component showed a significantly negative correlation (p<0.05) with the concentration of γ-HCH and p,p’-DDE. There were significant positive correlations (p<0.05) between the by-products of microbial degradation in DOM components and the concentration of heptachlor. There were also a significant positive correlation (p<0.05) between the content of active humus component of humic acid in the DOM and the concentration of heptachlor epoxide. These results suggested that the distribution of different types of pesticides residue in the soil was influenced by different components at different levels of significance. (3) The humification degree of soil organic matter showed minor effect of DOM on the pesticide residues in the soil. In this study, 3D-EEM and FRI technology were firstly coupled in use for studying the influence of different components of DOM in soil on the environmental behavior of pesticides, which provides a new idea for the research on the mechanism of pesticides transportation and transformation in soil and groundwater environment.