光活化高碘酸盐降解水中新烟碱农药吡虫啉性能研究

Performance of Photoactivated Periodate for the Degradation of the Neonicotinoid Pesticide Imidacloprid in Water

  • 摘要: 新烟碱农药包括吡虫啉、啶虫脒、呋虫胺等,通过干扰生物体内信号传递杀死害虫,在农业生产中广泛使用。进入水环境后,吡虫啉具有高溶解性、较长半减期的性质,其残留对生态安全和人体健康造成潜在风险,因此有必要开发此类污染物的高效降解技术。本文以吡虫啉为目标污染物,采用光活化高碘酸盐(UV/PI)技术,通过光化学模拟实验,考察不同水环境因子对吡虫啉降解效率的影响,揭示降解中涉及的主要活性物种,根据高效液相色谱-质谱联用(HPLC-MS)技术测定的结果,推测吡虫啉降解产物及路径,并评估了吡虫啉及其降解产物的生态风险。结果表明:①UV/PI体系中吡虫啉降解遵循一级反应动力学,PI浓度为5mmol/L时降解性能较好,90min内降解率为88.5%;PI浓度对降解的效果呈先增后缓趋势;弱碱性条件(pH=8)促进了吡虫啉降解,黄腐酸抑制了降解,硝酸根离子促进了降解;②单线态氧(1O2)和碘自由基(IO3、IO4)是吡虫啉降解的主要活性物种;降解路径主要涉及脱氯、羟基化和脱水氨化反应,降解产物有吡虫啉胍、6-氯烟酰酸、6-氯烟酰胺等;③吡虫啉中的咪唑基团、硝基亚氨基等基团破环后,部分降解产物急性毒性、发育毒性和诱变毒性降低,然而未完全矿化前仍存在生态风险。与传统的物理吸附、微生物降解等方法相比,本文通过UV/PI技术降解吡虫啉,相较于超声、活性炭等活化高碘酸盐技术,具有反应活性高、时间短、节约成本和环境友好等优势。本文成果对新烟碱类农药引发的水污染防治具有借鉴意义。

     

    Abstract: Neonicotinoid pesticides, including imidacloprid, acetamiprid, and thiamethoxam, are widely used in agricultural production to kill pests by disrupting signal transduction within organisms. Imidacloprid has the properties of high solubility and a long half-life after entering the aquatic environment, and its residues pose potential risks to ecological safety and human health. Therefore, it is necessary to develop efficient technologies to eliminate these contaminants. Here, imidacloprid is selected as the target pollutant. Photochemical simulation experiments and photoactivated periodate (UV/PI) technology were conducted to evaluate the effects of various water environmental factors on the degradation efficiency of imidacloprid and identify the major reactive species involved in the degradation process. Based on the results obtained from high performance liquid chromatography-mass spectrometry (HPLC-MS), the degradation products and pathways of imidacloprid were projected, and the ecological risks of imidacloprid and its degradation products were assessed. The results indicated that the degradation of imidacloprid in the UV/PI system followed first-order reaction kinetics. The degradation performance was optimal when the concentration of PI was 5mmol/L, with a degradation rate of 88.5% within 90min. The effect of PI concentration on the degradation rate followed a trend of initially increasing and then decreasing. A slightly alkaline condition (pH=8) and NO3 promoted the degradation of imidacloprid, while fulvic acid inhibited the degradation. Singlet oxygen (1O2) and iodine radicals (IO3·, IO4·) were the primary reactive species to degraded imidacloprid. The degradation pathways mainly involved dechlorination, hydroxylation, and dehydration amidation reactions. The degradation products included imidacloprid guanidine, 6-chloronicotinic acid, and 6-chloronicotinamide. After cleavage of groups such as the imidazole and nitroimine group in imidacloprid, acute toxicity, developmental toxicity and mutagenicity of some degradation products were reduced. However, the incomplete mineralization of these products still had ecological risks. Compared with traditional methods such as physical adsorption and microbial degradation, and other periodate activation methods such as ultrasonication and activated carbon, the degradation of imidacloprid using UV/PI technology in this study exhibits advantages including high reactivity, short reaction time, cost-effectiveness, and environmental friendliness. The findings provide valuable references for the prevention and control of water pollution caused by neonicotinoid pesticides. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202503140043.

     

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