壬基苯酚(nonylphenol, NP)結構式與雌性激素類似，具有高潛勢之生物內分泌干擾物質，被稱為環境荷爾蒙。壬基苯酚屬於疏水性(hydrophobicity)有機微污染物(log Kow = 4.48)，易與底泥中腐植化物質(humic substance, HS)產生鍵結，尤其是水溶性腐植酸(humic acid, HA)。本研究添加壬基苯酚(NP)以及添加0.02%乙基汞柳酸鈉(sodium ethylmercurthiosalicyclate, thimerosal)殺菌劑之河川底泥懸浮液，利用0.1 M HCl 及0.1 M NaOH調節其pH值為4.00，6.00及8.00，再分別添加腐植酸及黃酸(fulvic acid, FA)。於室溫下測定反應系統中壬基苯酚與腐植酸或黃酸的鍵結反應。另外，以自行研發設計且獲專利之氣體吸收及釋放反應瓶，於室溫(25℃)、滅菌及常壓下，於河川底泥中壬基苯酚有無添加腐植酸或黃酸經由δ-MnO2之氧化及礦化作用（mineralization）。研究指出添加δ-MnO2可促進壬基苯酚降解釋出CO2 。然而，添加腐植化物質會降低δ-MnO2對壬基苯酚 礦化釋出CO2，但是對壬基苯酚降解反而上升。以傅立葉轉換紅外線光譜儀(FT-IR)分析壬基苯酚與腐植化物質相互反應後，壬基苯酚之苯環結構產生結合轉移為其他產物。這明確指出底泥中腐植化物質會以非生物性緩慢破壞壬基苯酚，經添加δ-MnO2加速氧化及礦化壬基苯酚之苯環結構釋出CO2及其他產物， 減少壬基苯酚對環境潛在之危害。進而，以動力學及等溫吸附模式在不同pH值下，底泥中壬基苯酚和腐植化物質符合Dubinin–Radushkevich和Temkin之等溫吸附模式，以二階動力學反應為主。本實驗之數據及參數，可作為規劃整治河川底泥中壬基苯酚污染之方針。

Nonylphenol (NP) is a degraded product of nonylphenol polyethoxylate (NPnEO) mode surfactants which accounted for 80% of the non-ionized detergent used. It is widely proliferated in the streams and creeks of country because of illegal dumping into effluent waters of NPnEO surfactants. Since the structure of NP is similar to estrogen, NP possesses the ability to mimic natural hormones by interaction with estrogen receptors. It has been confirmed that, once NP runs into human body, it will decrease male sperm count and interfere normal metabolism. It will also reduce immunity, interfere physiology, and cause breast and testicular cancer when exposures at NP-contaminated environment in a long time. Nonylphenol would also reduce and inhibit estrogen efficacy in animals and zooplankton.
Manganese oxides are involved in many environmentally important minerals because they are strongly oxidizing and can affect the fate and transport of metals and organic compounds through oxidative/reductive reactions. Birnessite (its synthetic analogue is δ-MnO2) is an abundant naturally occurring mixed valence oxide. Natural organic matter (NOM) is ubiquitous in the environment and can be involved in the interaction between contaminants. Aquatic humicsubstances have a greater sorption capacity for nonylphenol. This work focuses primarily on the oxidation of nonylphenol in river sediments by δ-MnO2 (birnessite) and interaction with humic substances. The results showed that addition of δ-MnO2 to nonylphenol was mineralized and release CO2. However, addition of humic substances to nonylphenol in the presence of δ-MnO2 will reduce the decarboxylation and increase the nonylphenol degradation. Therefore, δ-MnO2 had good decomposition effects on nonyphenol in the presence of humic substances. Nonylphenol and humic substances interactions were analyses by FT-IR. The kinetics studies of adsorption isotherm at different pH values, of NP and HA in sediments was described by Dubinin-Radushkevich and Temkin adsorption isotherm models, and mainly pseudo-second -order kinetics.

目錄
摘要 I
Abstract III
致謝 V
目錄 V
表目錄 IX
圖目錄 XI
第一章 前言 1
1.1研究緣起 1
第二章 文獻回顧 5
2.1 壬基苯酚之來源與特性 5
2.2 環境中壬基苯酚之途徑及影響 6
2.3 腐植化物質對壬基苯酚之影響 11
2.4壬基苯酚之氧化處理 15
2.5二氧化錳介紹及應用 16
第三章 材料與方法 23
3.1 試驗底泥及石英砂 23
3.1.1 樣品採集及處理 23
3.1.2供試污染底泥及石英砂配製 24
3.1.3腐植化物質之萃取與純化 25
3.1.3 δ-MnO2之製備 27
3.1.2 儀器與藥品 29
3.2實驗方法 31
3.2.1底泥及石英砂基本性質分析 31
3.2.2配製污染底泥及石英砂之回收率 35
3.2.3腐植化物質之組成特性分析 35
3.2.4 微奈米級尺寸δ-MnO2特性分析 39
3.2.5 壬基苯酚與腐植化物質相互反應 39
3.2.6微奈米δ-MnO2氧化降解作用 42
3.2.7 自動滴定儀 45
3.2.8 HPLC定量分析 46
第四章 結果與討論 49
4.1底泥及石英砂之基本性質 49
4.2底泥及石英砂中壬基苯酚之回收率 50
4.3 δ-MnO 2尺寸鑑定 50
4.4腐植化物質分析組成特性 52
4.4.1元素分析儀分析結果 52
4.4.2 腐植化物質之全酸度與羧酸基 54
4.4.3傅立葉轉換紅外線光譜分析 55
4.4.4高效能雷射粒徑儀分析 58
4.5 添加壬基苯酚之河川底泥及對照組石英砂，在空氣下有無添加腐植化物質及δ-MnO2之氧化礦化反應 60
4.5.1二氧化碳釋放 61
4.5.2添加不同比例黃酸對壬基苯酚之礦化降解率 63
4.5.3礦化降解率 65
4.6 添加壬基苯酚之河川底泥及石英砂，在常溫下有無添加腐植化物質之相互反應 67
4.6.1不同pH值下，壬基苯酚與腐植化物質相互反應之殘留量 67
4.6.2 腐植化物質與壬基苯酚於底泥鍵結之官能基分析 71
4.6.2 相互反應之動力學 76
4.6.3等溫吸附平衡 83
第五章 結論與建議 95
參考文獻 97
附錄 110
表目錄
表2-1壬基苯酚物化特性 6
表2-1 壬基苯酚在各國河川底泥之濃度 10
表2-2底泥及土壤腐植化物質之元素組成 13
表3-1所使用之材料與藥品 29
表3-2所使用之儀器廠牌與型號 30
表3-3 HPLC分析條件 47
表4-1底泥及石英砂之基本性質 49
表4-2底泥元素分析及壬基苯酚含量 49
表4-3底泥及石英砂經八小時萃取連續三次之壬基苯酚回收率 50
表4-4腐植化物質之元素分析 53
表4-5腐植化物質中全酸度及羧酸基關係 54
表4-6 FT-IR 光譜主要吸收峰之鑑識 57
表4-7在空氣下經不同處理於污染石英砂之CO2釋放量 62
表4-8在空氣下經不同處理於污染底泥之CO2釋放量 63
表4-9在不同pH值下含壬基苯酚石英砂及底泥與0.5%腐植酸之0-30天動力學參數 79
表4-10在不同pH值下含壬基苯酚石英砂及底泥與0.5%腐植酸之0-10天動力學參數 80
表4-11在不同pH值下含壬基苯酚石英砂及底泥與0.5%腐植酸之10-20天動力學參數 81
表4-12在不同pH值下含壬基苯酚石英砂及底泥與0.5%腐植酸之20-30天動力學參數 82
表4-13添加腐植酸對含壬基苯酚底泥在pH 4.00, 6.00及8.00之等溫吸附模式推導 93
表4-14添加腐植酸對壬基苯酚在pH 4.00, 6.00及8.00之等溫吸附模式推導 94
圖目錄
圖1-1 研究架構 4
圖2-1 壬基苯酚環境分佈示意圖 8
圖2-2 壬基苯酚聚乙烯醇類降解途徑 9
圖2-3 壬基苯酚與雌激素(17β-estradiol)競爭荷爾蒙受體之機制 10
圖2-4 典型之腐植酸結構 14
圖2-5 壬基苯酚之裂解途徑 16
圖2-6不同合成的二氧化錳氧化物生成途徑及相互關係 17
圖2-7二氧化錳表面構造及其反應途徑 19
圖2-8鄰苯二酚與片錳礦物氧化過程之自由基反應 20
圖2-9 反應系統之pH主要流程 21
圖2-10 在25℃下以通氣及通氮氣下，經90小時δ- MnO2與苯酚類化合物之催化機制 22
圖3-1腐植酸(HA)及黃酸(FA)之萃取及純化之詳細流程 27
圖3-2 δ-MnO2製備流程 28
圖 3-3 土壤質地分類三角圖 34
圖3-4三角燒瓶相互反應組 41
圖3-5氣體吸收釋放反應瓶 44
圖3-6碳酸鹽系統在不同pH條件下的分佈圖 46
圖 3-7 NP之滯留時間 48
圖 3-8 NP之檢量線 48
圖4-1高效能粒徑分析儀(HPPS)分析鑑定δ-MnO2粒徑 51
圖4-2場發射掃描式電子顯微鏡(FE-SEM)分析鑑定δ-MnO2尺寸(100,000 X) 51
圖4-3 腐植化物質之紅外線光譜 56
圖4-4 腐植酸之高效能雷射粒徑儀分析 59
圖4-5黃酸(MW > 1000)之高效能雷射粒徑儀分析 59
圖4-6黃酸(MW < 1000)之高效能雷射粒徑儀分析 60
圖4-7 添加 δ-MnO2於石英砂(Q)及底泥(S)在不同比例黃酸(FA)下經由90小時震盪之壬基苯酚(NP)降解率 64
圖4-8石英砂(Q)及底泥(S)在有無添加δ-MnO2 (M)之壬基苯酚(NP)降解率 66
圖4-9石英砂(Q)及底泥(S)在有無添加δ-MnO2 (M)及黃酸(FA)或腐植酸(HA)之壬基苯酚(NP)降解率 66
圖4-10石英砂(Q)中壬基苯酚(NP)與腐植酸(HA)相互反應之殘留量 69
圖4-11底泥(S)中壬基苯酚(NP)與腐植酸(HA)相互反應之殘留量 69
圖4-12石英砂(Q)中壬基苯酚(NP)與黃酸(FA)相互反應之殘留量 70
圖4-13 底泥(S)中壬基苯酚(NP)與黃酸(FA)相互反應之殘留量 70
圖4-14壬基苯酚(NP)污染底泥(S)添加腐植化物質在pH 4.00在(a) 2小時(b) 20天之紅外線光譜 73
圖4-16 壬基苯酚污染之底泥添加腐植化物質在pH 8.00在(a) 2小時(b) 20天之紅外線光譜 75
圖4-17在不同pH值下含不同濃度壬基苯酚底泥與0.5%腐植酸之等溫吸附曲線 86
圖4-18在不同pH值下含不同濃度壬基苯酚溶液與0.5%腐植酸之等溫吸附曲線 86
圖4-19含不同濃度壬基苯酚底泥在(a) pH 4.00 (b) pH 6.00 (c) pH 8.00之等溫吸附模式 90
圖4-20含不同濃度壬基苯酚底泥與0.5%腐植酸在(a) pH 4.00 (b) pH 6.00 (c) pH 8.00之等溫吸附模式 91
圖4-21含不同濃度壬基苯酚溶液與0.5%腐植酸在(a) pH 4.00 (b) pH 6.00 (c) pH 8.00之等溫吸附模式 92

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