【作者】 赵建亮；

【导师】 张高勇； 秦勇；

【作者基本信息】 中国日用化学工业研究院 ， 应用化学， 2006， 硕士

【摘要】 本论文参照文献建立了测定壬基酚聚氧乙烯醚（NPEOs,NP_nEO中n表示平均EO数）初级生物降解度的新方法——卟啉法,通过加入NaOH解决了培养基溶液中NH₄⁺对Pb（II）-T（DBHP）P-NPEOs三元复合物在478 nm吸光度的抑制作用,并解决了加入NaOH后引起的沉淀问题,T（DBHP）P为四-（3,5-二溴-4-羟基苯基）-卟啉。卟啉法简便、快速,不需萃取,避免了乳化层的干扰,对ρ(NP₁₀EO)=5.0 mg·L^-1、10.0 mg·L^-1、20.0 mg·L^-1、30.0 mg·L^-1培养基溶液的回收率在96%¹01%,相对标准偏差<3%,最低检出限为0.2mg·L^-1。卟啉法适用于测定EO数5²0的NPEOs的生物降解度,硫氰酸钴法（CTAS法）适用于测定EO数≧10的NPEOs的生物降解度。振荡培养试验模拟NPEOs的好氧生物降解环境,以卟啉法测定了不同EO数NPEOs的质量浓度随降解时间的变化,2天内,各NPEOs的质量浓度都下降了98%以上。2天后,NP5EO和NP10EO的质量浓度不再变化;NP₁₅EO、NP₁₈EO、NP₂₀EO的表观质量浓度出现先增加再降低的现象,7天后NP₁₅EO的质量浓度与初始相比又降到98%,14天后NP₁₈EO和NP₂₀EO的质量浓度又降到90%;此现象与长EO链NPEOs降解生成的聚乙二醇对复合液的增敏作用有关。除去此增敏作用,得到不同EO数NPEOs的降解度随降解时间的变化,14天内初级生物降解度都超过90%,表明NPEOs易初级降解。以紫外可见分光光度法测定NPEOs中苯环的降解,8¹0天内移除率>80%,表明大部分NPEOs中的苯环可被微生物降解。高效液相色谱法测定结果与紫外可见分光光度法一致。电喷雾质谱法测定NPEOs及其降解中间体,表明:长EO链NPEOs通过ω/β-氧化途径或EO链断裂途径生成短EO链NPEOs。短EO链NPEOs在烷基链端ω-氧化生成CNPEO,继续β-氧化生成物质HOOC-C₆H₄-（OC₂H₄）_1²OH,最终降解为H₂O、CO₂等物质。并提出了NPEOs较完整的生物降解途径。通过筛选、分离、纯化得到9可能降解的NP₂EO中苯环的菌株,初步进行了鉴定,得到一株较高效的假单胞菌属菌株,10天内可将NP₂EO中40%左右的苯环降解。将高效的NP₂EO生物降解菌株用于污水处理厂的废水处理,非常具有意义。更多还原

【Abstract】 A fast and simple porphyrin method for determining primary biodegradabilities ofnonylphenol ethoxylates（NPEOs） was built, and the method did not require extraction. Themethod resolved the problem that absorbance of Pb（II）-T（DBHP）P-NPEOs complex at 478nm was restrained by NH₄⁺ in culture medium through adding NaOH. Average recoveries ofNP₁₀EO mass concentrations were between 96%¹01%, and relative standard deviations wereless than 3%, and detect limit was 0.2 mg·L^-1. And CTAS method was applicable for NPEOswith EO number more than 10, while porphyrin method was more fitted to NPEOs with EOnumber between 5 and 20.Aerobic biodegradation of NPEOs was tested in shaking-flask. Mass concentrations ofNP5²0EO changed with time were determined using porphyrin method, and all massconcentrations of NP_5²0EO decreased to 98% of initial concentrations in 2 days. After 2 day,mass concentrations of NP₅EO and NP₁₀EO remained unchanged, but concentrations oflong-EO-chain NPEOs increased firstly and decreased again. Mass concentration of NP15EOdecreased 98% again after 7 days, and those of NP18EO and NP₂₀EO decreased 90% after 14days. These phenomena were related to increasing-absorption effect of complex aroused bypolyglycol produced by long EO chain NPEOs during biodegradation. After the effects werededucted, all biodegradabilities of NPEOs were excess of 90% in 14 days, indicating primarybiodegradation of NPEOs were readily carried out.The biodegradation of benzene rings in NPEOs molecular was determined using UVspectrophotometer. The results shown that more than 80% of benzene rings were removedafter 8¹0 days of degradation. NP₂EO sample was also determined using HPLC, and thechanges of concentration of NPEOs were coincident with those determined by UV method.Biodegradation intermediates of NPEOs were also analyzed by ESI-MS. Long-EO-chainNPEOs was degraded to short-EO-chain by ω/β-oxidation or central fission pathway. Then,alkyl-chains of short-EO-chain NPEOs were shorted by ω/β-oxidation. The substance ofHOOC-C₆H₄-（OC₂H₄）_1²OH was detected during degradation, which indicated alkyl-chains ofNPEOs took place and degraded ultimately. A complete aerobic biodegradation pathway ofNPEOs was proposed on the basis of UV, HPLC and ESI-MS results.Nine strains were obtained by step of selection, separation and purification. 40% benzenerings in NPEOs were removed by a relative high-effected strain （Pseudomonas sp.）. The strainof benzene rings biodegraded could be applied to wastewater plants, and it is meaningful toour society.更多还原