【作者】 胡继业；

【导师】 张文吉；

【作者基本信息】 中国农业大学 ， 农药学， 2004， 博士

【摘要】 o-烯丙基苯酚、p/o-丁酰基苯酚是我国新研制的仿生合成杀菌剂。本文研究了它们的环境化学行为和对土壤微生物的生态效应，为其环境和生态评价提供科学依据。 建立了o-烯丙基苯酚、p/o-丁酰基苯酚的残留分析方法并研究了其在番茄中的消解动态和最终残留。番茄经丙酮提取，液-液分配净化，o-烯丙基苯酚用弗罗里硅土、p/o-丁酰基苯酚用酸洗活性炭进一步净化，浓缩、定容后，用带紫外检测器的高效液相色谱进行测定。最低检出量为3ng，在番茄中的最低检出浓度是0.01mg／kg。添加回收率为87.7％～95.1％，变异系数1.22％～2.57％，符合农药残留分析要求。运用上述方法，测定了在番茄中的消解动态以及最终残留。结果表明：o-烯丙基苯酚在番茄中的半衰期为6.37d，番茄收获时消解在80％以上；p/o-丁酰基苯酚的半衰期为4.15d，番茄收获时，消解在90％以上，降解速率中等。 以太阳光和紫外灯为光源研究了o-烯丙基苯酚以及p/o-丁酰基苯酚的两个异构体在溶液相中的光化学降解。太阳光下，o-烯丙基苯酚在甲醇、正己烷、重蒸水以及不同pH的缓冲溶液中的光稳定性很强，但在丙酮中可以光解，104mg／L的o-烯丙基苯酚在丙酮中的光解半衰期为36.4h；10mg／kg的核黄素、三氯化铁、过氧化氢，均对o-烯丙基苯酚在重蒸水中的光解有不同程度的光敏化作用。p-丁酰基苯酚在甲醇、正己烷中能稳定存在，阳光照射40h浓度无变化，在丙酮中光降解显著，129.4mg／L的p-丁酰基苯酚丙酮溶液的光照40h，光解率为46.2％；p-丁酰基苯酚在重蒸水中有一定程度的光解，20mg/L的p-丁酰基苯酚的重蒸水溶液，阳光照射40h，其光解率为50.58％。核黄素、过氧化氢对p-丁酰基苯酚的光解有显著的敏化作用，光照8h，p-丁酰基苯酚的光解率分别为96.42％和95.0％，而三氯化铁则对其光解有一定的抑制作用。o-丁酰基苯酚的甲醇、正己烷溶液在太阳光下分别有轻微光解，而在丙酮中显著光解，138.8 mg／L o-丁酰基苯酚的丙酮溶液光照40h，光解率为95.1％。核黄素对o-丁酰基苯酚的光解有显著的敏化作用，光照8h，o-丁酰基苯酚的光解率为92.35％。过氧化氢、三氯化铁对o-丁酰基苯酚的光解有一定程度的敏化作用，光照40h，其光解率分别为73.1％和19.19％。在紫外光照下，这两种杀菌剂在各种溶剂中光解迅速，速率遵循一级动力学方程；水中溶解物质对其光解有一定的抑制作用；在不同pH值缓冲溶液中的光解速率为pH=9中光解最快。紫外光照2h，o-烯丙基苯酚在甲醇中的主要光降解产物鉴定为：2，4，5-三羟基苯甲醛、o-羟基苯乙酸甲酯、p-烯丙基苯酚、2，3-二氢-2-甲基苯并呋喃；p-丁酰基苯酚在甲醇中紫外光照4h，其降解产物鉴定为2，4，5-三羟基苯甲醛。 实验室条件下，通过对东北黑土、北京褐土、江西红土中添加o-烯丙基苯酚、p/o-丁酰基苯酚的降解研究发现：微生物对其在3种土壤中的降解起主要作用，它们在未灭菌土中的降解速度很快，符合一级动力学方程，T_0.5在10.26h～2.51d之间。两者均在有机质含量较高、pH偏碱性的东北土壤中降解最快。土壤含水量增加，降解速度减慢；外加碳源的存在，并没有加快它们的降解速度；在土壤中被微生物彻底矿化为CO₂等小分子化合物，不会对土壤造成累积性污染。 实验室条件下研究了o-烯丙基苯酚、p/o-丁酰基苯酚在不同温度和不同pH条件下的灭菌水中化学水解以及在生态水环境中的降解。结果表明，无论在25℃还是35℃，在不同pH值缓冲溶液和氢氧化钠溶液中，50d浓度均无衰减趋势，极难化学水解。在鱼塘水中也能稳定存在，50d内没有降解趋势，水体中的微生物不能使其降解，因此它们可能会对水体造成污染。 研究了。一烯丙基苯酚、P/o一」‘酞基苯酚对土壤微生物活性的影响。它们在所设计的浓度卜，对一仁壤呼吸作用、过氧化氢酶和腮酶活性没有显著影响。对土壤防线菌数量没有影响;o一烯丙基苯酚对真菌数量的影响表现为先刺激，后逐渐恢复;尸劝一J一酞基苯酚则对真菌数量影响不大。两者对细菌数量的影响则为先抑制，_且随浓度增大抑制作用增强，后逐渐恢复稳定。总之，两者对十壤微生态系影响不人。更多还原

【Abstract】 o-Allyphenol and p/o-Butanoylphenol which are new fungicides simulated the active compounds structure in Gingko (Gingko biloba L). were exploited and developed by our own country. Our subjects were to study the chemical behavior of them in environment and ecological effects on soil microbe in order to supply the scientific evidence of the enviromental and ecological safty evaluation.The methods of residual analysis, dissipation and final residues of o-Allylphenol and /j/o-Butanoylphenol in tomato were studied. Residues were extracted from tomato with acetone, purified by liquid-liquid partition, and o-AUyphenol was further purified with Florisil, p/o-Butanoylphenol with active carbon, and then concentrated to a small volume, determined by HPLC equipped with UV-detector. The minimum detectable amount of o-Allylphenol and p/o-Butanoylphenol was 3ng, the minimum detectable concentration of them in the samples of tomato were 0.01mg/kg. The average recoveries and coefficient variation of the method were 87.7%~95.1% and 1.22%~2.57%, respectively. The dissipation and final residues in tomato were determined with the method described above. The results showed that the half-life of o-AHylphenol in tomato was 6.37 days, and o-Allylphenol dissipated by 80% in tomato at tomato harvest. The half-life of p/o-ButanoyIphenol in tomato was 4.15 days, and it dissipated by 90% in tomato at tomato harvest. Their rates of dissipation were medium.The photo-degradation of o-Allylphenol and p/o-Butanoylphenol by UV irradiation or sunlight in various solvents was examined. Under sunlight, o-Allylphenol decomposed very slowly in aqueous phase, w-hexane and methanol, but decomposed easily in acetone with half-life of 36.4h of o-Allylphenol of 104mg/L. Photosensitizer such as riboflavin, H2O2 and Fe+3, can enhance photolysis of o-Allylphenol in aqueous solutions. /7-Butanoylphenol decomposed very slowly in n-hexane or methanol, and relatively faster in acetone with 46.3% of 129.4 mg/L /M-Butanoylphenol decomposed by 40 hours irradiation .p-Butanoyl phenol of 20mg/kg decomposed by 50.58% in aqueous phase by 40 hours irradiation, riboflavin and H2O2 can enhance photolysis of it distinctively with 96.42% and 95.0% decomposed, respectively, by 8 hours irradiation, while Fe+3 restrained photolysis of it. o-Butanoylphenol decomposed slightly in H-hexane or methanol, and quickly in acetone with 95.1% of 138.8 mg/L o-Butanoylphenol in acetone decomposed by 40 hours irradiation in sun light. Riboflavin can enhance photolysis of o-Butanoylphenol in aqueous phase distinctively with 92.35% decomposed by 8 hours irradiation, H2O2 and Fe+3 enhance photolysis of it relatively slightly with 73.1% and 19.19% decomposed, respectively, by 40 hours irradiation. Under UV light, o-Allylphenol and p-Butanoylphenol readily photo-degraded in various solvents, and the rate of photo-degradation of them followed first-order kinetics with significant correlation coefficient. They decomposed most quickly in pH=9 aqueous buffered samples, and also dependent upon the dissolved impurities which slowed the rate of the photo-degradation. Four major photoproducts of o-Allylphenol in methanol by 2h UV irradiation were detected and tentatively identified as: 2,4,5-TrihydroxybenzaIdehyde, p-Allylphenol, Methyl 2-hydroxphenylacetate,2-methyl-benzodihydrofuran. The major photoproduct of p-Butanoylphenol in methanol by 4 hours UV irradiation was identified as: 2,4,5-Trihydroxybenzaldehyde.Under laboratory conditions, degradation of o-Allylphenol and p/b-Butanoylphenol in 3 soils including Black Soil from Northeast China, Cinnamon soil from Beijing, and Red soil from Jiangxi Province of China was studied. The results showed that the bio-degradation of o-AUylphenol andp/o-Butanoylphenol in these 3 soils was playing a leading role and taking place easily in unsterilized soil, T0.5 was among 10.26h~2.51d. They degraded most quickly in Black soil in which microbe was more active, since Black siol has much organic matter and is alkialine soil. The rate follows a pseudo更多还原