猪粪沤肥过程中磺胺甲恶唑及其代谢产物的变化规律

    Study on the degradation of sulfamethoxazole and its metabolites in pig manure during the facultative anaerobic composting process

    • 摘要: 磺胺甲恶唑(sulfamethoxazole, SMX)是畜禽养殖业中常用的兽用抗生素,其性质稳定,随畜禽粪污排放到环境后可长期残留,同时其在环境中降解后产生的部分代谢产物毒性显著高于母体化合物,现有研究多关注SMX本身在环境中的残留情况,对其高毒性代谢产物的关注较少。我国生猪养殖规模居世界首位,堆沤是猪粪的主要无害化处理方式。该研究分析了不同堆沤温度(35、25、15 ℃)及不同原料初始含水率(70%、75%、80%)条件下SMX在猪粪堆沤过程中的降解及其7种重要代谢产物的变化情况,结果表明:各试验组在90 d的堆沤发酵后,SMX的降解率在64.82%~78.04%之间,在堆沤温度为35 ℃、原料初始含水率80%条件下SMX的降解率最高,表明高温和高含水率有利于SMX的降解;共有6种SMX代谢产物被检出,其中3-氨基-5-甲基异恶唑是主要的代谢产物,检出浓度最高可达4.13 mg/kg,根据结构特征分析,推测该化合物可能通过细菌代谢过程中的S-N键断裂途径生成;2种高毒性代谢产物(4-羟基-磺胺甲恶唑和4-硝基-磺胺甲恶唑)被检出,检出最高浓度分别达到0.12和0.03 mg/kg,其中4-硝基-磺胺甲恶唑在25 ℃下的生成浓度最高,4-羟基-磺胺甲恶唑的产生受温度和初始含水率影响不明显。该研究通过综合分析,提出采取定期翻堆或通风、维持堆沤温度在30 ℃以上等措施,可能对降低2种SMX高毒性代谢产物的产生有一定促进作用。该研究结果对促进生猪粪便无害化处理、提升畜禽粪污资源化利用水平提供了技术支撑。

       

      Abstract: The annual total amount of livestock and poultry manure produced in China can reach approximately 3.05 billion tons. Among them, pigs, as one of the main types of livestock raised, have a large number of animals in stock and a wide range of breeding areas. The amount of pig manure accounts for a relatively high proportion of the total manure produced by livestock and poultry in China. Therefore, the treatment of pig manure has become a key focus in the pollution control and prevention of breeding industry in China. Antibiotics are widely used in livestock and poultry breeding industry for therapeutic and disease prevention. Veterinary antibiotics administered to animals in the breeding industry are not completely metabolized by the animals. Approximately 20% to 97% of these antibiotics are excreted in their active forms via manure, leading to antibiotic residues in the environment and posing threats to ecosystems and human health. Sulfamethoxazole (SMX) is a widely used veterinary antibiotic in the livestock and poultry breeding industry. Due to its stable chemical properties, it can persist in the environment long-term after being discharged via livestock manure. Furthermore, some degradation metabolites of SMX in the environment exhibit significantly higher toxicity than the SMX itself. Among them, the toxicity of 4-hydroxyl-N-(5-methyl-1,2-oxazole-3-yl)benzene-1-sulfonamide (4-OH-SMX) and 4-nitro-sulfamethoxazole (4-NO2-SMX) is 5.7 times and 21.4 times that of SMX respectively. Previous researches primarily focused on the residual levels of SMX in the environment, with less attention given to its higher toxic metabolites. China is the world's largest pork producer, facultative anaerobic composting is a major method for the harmless treatment of pig manure. This research comprehensively investigates the degradation dynamics of SMX and its seven important metabolites during the facultative anaerobic composting process of pig manure. The study systematically evaluated the influence of varying ambient temperatures (35 ℃, 25 ℃, 15 ℃) and distinct initial moisture contents of the raw manure substrate (70%, 75%, 80%) on these processes over a defined experimental period. Following a 90-day facultative anaerobic composting process across all tested conditions, the results demonstrated a substantial degradation efficiency for SMX, ranging from 64.82% to 78.04%. Notably, the most effective SMX removal was achieved under the combined conditions of 35 ℃ composting temperature and 80% moisture content, highlighting the synergistic enhancement of SMX degradation facilitated by elevated temperatures coupled with higher moisture levels. Analysis of metabolic transformation pathways revealed the detection of six distinct SMX metabolites throughout the facultative anaerobic composting precesses. Among them, 3-amino-5-methylisoxazole emerged as the predominant transformation product, reaching a peak detected concentration of 4.13 mg/kg. Its formation pathway was predicted by detailed structural characterization, which involving the enzymatic cleavage of the S-N bond within the parent SMX molecule, likely mediated by specific bacterial metabolic activities inherent to the composting microbiome. Critically, the study also identified the presence of 2 highly toxic metabolites, 4-OH-SMX and 4-NO2-SMX after composting. The maximum detected concentrations of 4-OH-SMX and 4-NO2-SMX were 0.12 mg/kg and 0.03 mg/kg, respectively. An important observation was that the generation of 4-NO2-SMX exhibited a temperature dependency, with its highest formation concentration occurring specifically at 25 ℃. Comparatively, the production of 4-OH-SMX behaved lower sensitivity to fluctuations in either composting temperature or the initial moisture content of the manure. This key finding indicates that the inherent biochemical pathways leading to 4-OH-SMX formation are remarkably persistent under standard composting conditions and cannot be effectively suppressed or avoided solely through temperature or moisture adjustments within the ranges tested. Consequently, the unavoidable presence of 4-OH-SMX necessitates the implementation of additional, targeted post-composting treatment strategies to effectively mitigate this residual toxicity and significantly enhance the overall environmental safety and suitability of the final compost product for subsequent agricultural utilization. Therefore, it is suggested in this study that turning or aerating the compost piles during the facultative anaerobic process, coupled with maintaining the temperature above 30 ℃, could probably help reduce the production of these highly toxic transformation products. In conclusion, the empirical findings and mechanistic insights proposed in this study offer substantial and actionable technical support for optimizing pig manure treatment protocols and provide a scientific basis for designing manure management strategies aimed at maximizing the degradation efficiency of residual SMX antibiotics while simultaneously minimizing the accumulation and potential environmental risks posed by its highly toxic transformation products, ultimately promoting safer resource utilization of pig manure.

       

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