臺灣博碩士論文加值系統

摘要
本實驗是以採自基隆河大佳河濱公園畔之底泥來偵測各種喹啉與吡啶及其含甲基或乙基衍生物在底泥中之降解情形，發現在厭氧硫酸還原狀態下，quinoline、3-methylquinoline、4-methylquinoline、nicotinic acid、pyridine、2-methylpyridine、3-methylpyridine、4-methylpyridine、2-ethylpyridine、3-ethylpyridine、4-ethylpyridine、2,4-dimethylpyridine、2,6-dimethylpyridine及3,5-dimethylpyridine各自皆能降解。而經過4-methylquinoline馴化過的底泥，能加快quinoline、3-methylquinoline與4-methylquinoline之降解；且似乎能改變nicotinic acid之降解途徑；但對3-methylpyridine與4-methylpyridine之降解則沒有幫助反而有所抑制。同樣地經過3-methylquinoline馴化的底泥對3-methylpyridine與4-methylpyridine之降解同樣沒有幫助反而有所抑制。另外經過3-methylpyridine或4-methylpyridine馴化過的底泥，與未經馴化的底泥來作比較，發現對2-ethylpyridine與3-ethylpyridine之降解並沒有多大幫助。但經過3-methylpyridine或4-methylpyridine馴化底泥對2-methylpyridine、2,4-dimethylpyridine、2,6-dimethylpyridine與3,5-dimethylpyridine的降解速率有增快之情形。而4-ethylpyridine只有經過3-methylpyridine馴化底泥對其降解有所幫助，但對於經過4-methylpyridine馴化底泥則不會幫助其降解。上述各類化合物在降解過程中只有quinoline、3-methylquinoline與4-methylquinoline的中間產物被偵測出。依據過去的報告得知，這些中間產物分別是在quinoline環上第2個C上被羥基化之產物。過去雖有報告指出羥基化亦是methylpyridines在厭氧降解過程中的第一個步驟，但在本論文研究中並未發現與確認有這些產物，雖然從這些化合物在降解過程中其可見光-紫外光吸收圖譜的變化得知它們的降解變化。若羥基化是這類化合物在厭氧降解過程中的第一個步驟，則由以上的馴化實驗可以看出烷基的位置似乎會影響羥基化的位置與速率。不過將上述各類化合物在底泥中的最快降解速率及t1/2降解速率或半衰期（t1/2）與它們的pKa值或log Kow值做一比較，發現它們之間並未有相關性。

目錄
中文摘要------------------------------------------------------------------------------------1
英文摘要------------------------------------------------------------------------------------3
第一章 前言------------------------------------------------------------------------------4
第一節 研究背景-------------------------------------------------------------4
第二節 前人研究------------------------------------------------------------10
第三節 研究內容與目的---------------------------------------------------13
第二章 材料與方法--------------------------------------------------------------------15
第一節 實驗材料-----------------------------------------------------------15
第二節 儀器設備-----------------------------------------------------------17
第三節 實驗方法-----------------------------------------------------------19
第四節 實驗內容-----------------------------------------------------------25
第三章 結果-----------------------------------------------------------------------------30
第一節 實驗品管-----------------------------------------------------------30
第二節 quinoline、pyridine衍生物在硫酸還原狀態底泥中之生物降解-------------------------------------------------------32
第四章 討論------------------------------------------------------------------------------58
第五章 結論------------------------------------------------------------------------------65
第六章 參考文獻------------------------------------------------------------------------69
表1-1 quinoline、pyridine衍生物之物性與化性--------------------------------74
表1-2 quinoline、pyridine衍生物之CAS RN、log Kow值、pKa值-------------------------------------------------------76
表1-3 分離出6種不同菌株分別進行有氧代謝14種不同的pyridine衍生物，所呈現不同的分解能力----------------------------------------------------------78
表1-4 7種已馴化的底泥分別進行厭氧代謝13種quinoline、pyridine衍生物，
所呈現的降解能力-------------------------------------------------------------78
表3-1 標準品回收率-------------------------------------------------------------------79
表3-2 quinoline、pyridine衍生物標準品以HPLC分析之滯留時間------------------------------------------------------80
圖1-1 quinoline、pyridine衍生物之結構------------------------------------------81
圖1-2 環境中石化污染物之污染源---------------------------------------------83
圖3-1 溶劑與quinoline、pyridine衍生物之HPLC分析圖譜------------------84
圖3-2 quinoline、pyridine衍生物以HPLC分析之檢量線----------------------89
圖3-3 硫酸根離子之檢量線-----------------------------------------------------------91
圖3-4 （a）在硫酸還原狀態之底泥中，4-methylquinoline之降解情形（b）
4-methylquinoline在經4-methylquinoline馴化之底泥中硫酸還原狀態下之降解情形（c）在經4-methylquinoline馴化之硫酸還原狀態底泥中，4-methylquinoline之降解情形----------------------------------------------92
圖3-5 （a）在硫酸還原狀態之底泥中，quinoline之降解情形（b）在經4-methylquinoline馴化之硫酸還原狀態底泥中，quinoline之降解情形
---------------------------------------------------------93
圖3-6 （a）在硫酸還原狀態之底泥中，3-methylquinoline之降解情形（b）
3-methylquinoline在經3-methylquinoline馴化之底泥中硫酸還原狀態下之
降解情形（c）在經4-methylquinoline馴化之硫酸還原狀態底泥中，
3-methylquinoline之降解情形-------------------------------------------------94
圖3-7 （a）在硫酸還原狀態之底泥中，nicotinic acid之降解情形。（b）在經4-methylquinoline馴化之硫酸還原狀態底泥中，nicotinic acid之降解情形
---------------------------------------------------95
圖3-8 （a）3-methylpyridine在經3-methylpyridine馴化之底泥中硫酸還原狀態下之降解情形（b）在經4-methylquinoline馴化之硫酸還原狀態底泥中，3-methylpyridine之降解情形（c）在經3-methylquinoline馴化硫酸還原狀態底泥中，3-methylpyridine之降解情形------------------------------------96
圖3-9 （a）4-methylpyridine在經4-methylpyridine馴化之底泥中硫酸還原狀態下之降解情形（b）在經4-methylquinoline馴化之硫酸還原狀態底泥中，4-methylpyridine之降解情形（c）在經3-methylquinoline馴化硫酸還原狀態底泥中，4-methylpyridine之降解情形------------------------------------97
圖3-10（a）在硫酸還原狀態之底泥中，2-methylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，2-methylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，2-methylpyridine之降解情形------------------------------------------------------------------------98
圖3-11（a）在硫酸還原狀態之底泥中，2-ethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，2-ethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，2-ethylpyridine之降解情形-----------------------------------------------------------------------99
圖3-12 （a）在硫酸還原狀態之底泥中，3-ethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，3-ethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，3-ethylpyridine之降解情形----------------------------------------------------------------------100
圖3-13 （a）在硫酸還原狀態之底泥中，4-ethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，4-ethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，4-ethylpyridine之降解情形----------------------------------------------------------------------101
圖3-14 （a）在硫酸還原狀態之底泥中，2,4-dimethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，2,4-dimethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，2,4-dimethylpyridine之降解情形--------------------------------------------102
圖3-15 （a）在硫酸還原狀態之底泥中，2,6-dimethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，2,6-dimethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，2,6-dimethylpyridine之降解情形--------------------------------------------103
圖3-16 （a）在硫酸還原狀態之底泥中，3,5-dimethylpyridine之降解情形（b）在經3-methylpyridine馴化之硫酸還原狀態底泥中，3,5-dimethylpyridine之降解情形（c）在經4-methylpyridine馴化之硫酸還原狀態底泥中，3,5-dimethylpyridine之降解情形--------------------------------------------104
圖3-17 （a）在經3-methylpyridine馴化之硫酸還原狀態底泥中，pyridine之降解情形（b）在經2,4-dimethylpyridine馴化之硫酸還原狀態底泥中，2-methylpyridine之降解情形（c）在經2,4-dimethylpyridine馴化之硫酸還原狀態底泥中，4-methylpyridine之降解情形。-------------------------105
圖3-18 （a）在經2,6-dimethylpyridine馴化之硫酸還原狀態底泥中，2-methylpyridine之降解情形（b）在經3,5-dimethylpyridine馴化之硫酸還原狀態底泥中，3-methylpyridine之降解情形-------------------------------------------------106
圖3-19 所有未經馴化與馴化底泥混合水的t1/2與最快降解速率---------------107
圖3-20 pyridine衍生物之分光光度計分析圖譜------------------------------------112
圖3-21 14種quinoline、pyridine衍生物之pKa值與t1/2和最快降解速率之關係
--------------------------------------------------115
圖3-22 14種quinoline、pyridine衍生物之log Kow值與t1/2和最快降解速率之關係------------------------------------------------------------------------116
圖3-23 14種quinoline、pyridine衍生物之t1/2與pKa值、log Kow值之關係
--------------------------------------------------117

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