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基于分子动力学模拟的猪粪中土霉素水热降解过程机理

Mechanism of oxytetracycline hydrothermal degradation process in pig manure based on molecular dynamics simulation

  • 摘要: 抗生素在畜禽养殖业中被广泛用于提高其抗病能力及生长速率,但残留的抗生素会通过粪便进入水土环境,进而对生态环境构成潜在威胁。传统的粪便处理方式对抗生素的降解周期长且效果有限,水热处理对抗生素具有明显的降解效果。该研究以猪粪中残留抗生素占比最高的土霉素为研究对象,使用Materials Studio软件建立并优化土霉素-水模型体系,利用LAMMPS软件对其进行水热过程的分子动力学模拟,分析了体系中水和羟基自由基的变化趋势及其在反应中的作用机制,探究了水热体系内土霉素水热降解的演变规律及水热反应路径。结果表明:土霉素的水热降解过程包括快速增长与缓慢增长两个阶段,且随着模拟温度增加,土霉素分子分解加剧。在模拟温度为1 800~2 000 K区间内,体系中土霉素降解产生的分子片段总数增长缓慢,而当温度进一步升高至2 200 K时,体系中土霉素降解产生的分子片段总数显著增多,其中长碳骨架片段比例由1 800 K的51.52%降至3 000 K的6.82%,而短链及小分子产物比例由45.45%升至80.68%。水热过程初期温度,体系中的H2O分子数低于初始值,此时土霉素主要发生水解反应,而随着模拟温度的增加,体系中的H2O分子数逐渐增多,表明水热温度的增加促进了体系中的脱水反应。随着模拟温度提高,体系中羟基自由基数量增多并在更高数目区间内波动,促进了土霉素发生脱甲基、脱氨基、脱水、羟基化、开环等反应,而降解成为小分子物质。

     

    Abstract: Antibiotics have been widely used to enhance disease resistance and growth rate in the livestock and poultry breeding industry. However, residual antibiotics can enter the water and soil environment via manure, easily leading to an increase in bacterial resistance to the environment. Thus, it is often required to remove residual antibiotics from the ecological environment. Conventional fecal treatments cannot fully meet the large-scale production in recent years, such as aerobic composting and anaerobic fermentation, due to the long degradation cycles and limited effects on antibiotics. In contrast, an efficient thermochemical conversion, hydrothermal treatment, can be expected to effectively promote the rapid and complete degradation of antibiotics. This study aims to simulate oxytetracycline hydrothermal degradation in pig manure using molecular dynamics. Oxytetracycline, which has the highest proportion of antibiotic residues in pig manure, was selected as the research object. The oxytetracycline-water model was established and then optimized using Materials Studio software. The degradation of oxytetracycline was conducted under hydrothermal conditions using molecular dynamics simulation with LAMMPS software and the ReaxxFF reaction force field. The hydrothermal degradation of oxytetracycline was explored in the hydrothermal system and the reaction path. A systematic analysis was implemented to explore the trends of water and hydroxyl radicals and their reaction mechanisms. Results indicate that hydrothermal temperature was the critical factor controlling oxytetracycline degradation. As the temperature increased, long-chain oxytetracycline molecules progressively fragmented into short-chain small-molecule fragments: The proportion of C1-5 fragments rose from 45.45% at 1 800 K to 80.68% at 3 000 K, while the proportion of complex long-chain molecules with C>15 decreased from 51.52% to 6.82%. The hydrothermal degradation of oxytetracycline was characterized by rapid and slow increases in fragment formation, and then molecular decomposition intensified with rising simulation temperature. In the temperature range of 1 800 K to 2 000 K, there was a low increase in the total number of molecular fragments produced by the degradation of oxytetracycline. In contrast, there was a significant increase in temperature over 2 200 K. The number of H2O molecules was closely related to the dominant reaction types, lower than the initial value in the initial stage of the reaction at a lower hydrothermal temperature (1 800~2 200 K). Oxytetracycline also shared the hydrolysis reaction. The number of H2O molecules gradually increased as the hydrothermal temperature rose, and a dehydration reaction also occurred. In addition, the number of hydroxyl radicals gradually increased and fluctuated within a higher range as the hydrothermal temperature increased. These hydroxyl radicals preferentially attacked high-electron-density active sites on the oxytetracycline molecule, thus promoting a series of complex reactions, such as demethylation, deamination, dehydration, hydroxylation, and ring-opening of oxytetracycline. Ultimately, there was the degradation of oxytetracycline into small-molecule substances. Molecular dynamics can be expected to explain the hydrothermal degradation of oxytetracycline at the molecular level. This finding can also provide theoretical guidance and perspective for the efficient removal of antibiotics from swine manure.

     

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