采用密闭瓶二氧化碳法对有机污染物的好氧生物降解性研究
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摘要
化学农药主要是人工合成的生物外源性物质,很多农药本身对人类及其它生物是有毒的,而且很多类型的农药残留物很难降解。这使农药在农业生产中的过分使用产生了严重的负面影响,生物降解不仅是有机化合物在环境中最重要的去除途径之一,而且还是化学元素循环的关键环节。因此,有机化合物的生物降解性能是评价化合物环境归宿和危害的重要指标。
     本研究依据经济合作与发展组织(OECD)化学品测试准则209及2006年3月正式颁布的快速生物降解试验310,在本实验室条件下建立了密闭瓶二氧化碳法,并对影响此方法的主要因素进行了详细地研究,另外还研究了活性污泥活性测定方法。本试验中以3,5-二氯苯酚、苯甲酸钠和苯胺为参比物,对新型杀菌剂氟吗啉和除草剂乙草胺的微生物毒性、快速生物降解性能进行了评价。
     试验结果表明,在本实验室条件下建立的密闭瓶二氧化碳法具有可行性。本试验选用苯甲酸钠作为参比物,苯甲酸钠在第4天的降解率就达到了62.09%,符合OECD实验准则的要求,说明试验可行,活性污泥的活性满足试验要求。同时也研究了另一种参比物苯胺,在第7天时的降解率为63.46%,也符合准则规定。因此苯甲酸钠和苯胺都可以作为本试验的参比物来选择。应用该方法评价了杀菌剂氟吗啉和除草剂乙草胺的快速生物降解性能,两种物质均不具备快速生物降解性。此外研究了三种因素对密闭瓶二氧化碳法的影响,可以得出,1.地表水、土壤浸出液、活性污泥这三种接种物由于所含微生物数量和种类的不同,最终所得出的苯甲酸钠和苯胺的降解率也明显不同,活性污泥的活性大于土壤浸出液,地表水活性最差。2.当接种物浓度大于40mg/L时,苯甲酸钠在第14天的降解率小于60%,不符合试验中关于参比物的规定。3.当苯甲酸钠浓度为5-40mgC/L时,降解率在第14天时均超过了60%, 20mgC/L浓度组的降解率最高,达到了85.35%,而100mgC/L和200mgC/L浓度组第14天的降解率均小于60%。在采用活性污泥呼吸抑制试验评价氟吗啉和乙草胺对活性污泥的毒性时,两者的EC50浓度大于300mg/L,两种物质对活性污泥没有毒性。在对接种物活性研究中发现随着驯化期的延长,接种物活性也在降低。
Chemical pesticide is mainly organism exogenous material which is synthesized by human beings. Many pesticides themselves are not only poisonous to the mankind and other creature but also very difficult to degrade. It caused serious negative influence when the pesticide is used excessively in the agricultural production. Microbial degradation is not only one of the most important transformation mechanisms for organic chemicals, but also a key process for the chemical recycling in the environment. Hence, biodegradation rates play an important role in estimation of the environment fate and hazard of chemicals.
     According to the Organization for Economic Co-operation and Development guideline for the testing of chemicals No. 310 CO2 in Sealed Vessels which was protrusived in March 2006、International Standard ISO 14593 (adopted March 1999) and the US Environmental Protection Agency (EPA), Office of Prevention, Pesticides and Toxic Substances, (OPPTS) Method 835.3120, we established the method No 310 CO2 in Sealed Vessels and studied the main factors in detail which had influence to this method, also studied the activeness of active sludge determination method. In this text, we evaluated the toxicity、the ready biodegradability of Flumorph and acetochlor, 3,5-dichlorophenol、sodium benzoate and aniline being the used reference compounds.
     The results of the research showed that it was feasible to evaluate the ready biodegradability using CO2 in Sealed Vessels Test established in this lab. In this text, we use sodium benzoate as the reference compound, sodium benzoate had been biodegraded by 62.09% by day 4, it proved the test was feasible and activeness of active sludge satisfiesd the experimental request. Another reference compound, aniline had been biodegraded by 63.46% by day 7,it also conformed to the OECD experiment criterion requirement. As a result, we could consider both sodium benzoate and the aniline as the reference compound. we evaluated the ready biodegradability of Flumorph and acetochlor, they are not considered readily biodegradable. We got three conclusions through studying the three factors influence to this method.1. the degeneration rate of sludge sodium benzoate and the aniline are obviously different because the three inoculums -surface water、soil leachate and active are different in the number of inoculum and the kind. The activity of active sludge exceeds the soil leachate , the surface water is the worst. 2. when the concentration of inoculum exceeded 40mg/L, sodium benzoate had been biodegraded less than 60% by day 14. the result doesn’t conformed to the OECD experiment criterion requirement about reference compound. 3. when the concentration of sodium benzoate was 5-40mgC/L, it’s degeneration had been exceeded 60% after 14 d, the group 20mgC/L was the best in degeneration, it was
     85.35%, the degeneration rate of group 100mgC/L and 200mgC/L had been biodegraded less than 60% by day 14. We evaluated the toxicity of Flumorph and acetochlor to active sludge using Activated Sludge Respiration Inhibition Test, both of theirs EC50 exceeded 300mg/L. It showed that they had no toxicity to active sludge. In the study of the activeness of active sludge, we learned the activeness of active sludge was descending when the time of acclimatization was longer.
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