在現今醫療科技進步且社會醫療福利完善的社會中，藥品及個人保健用品(Pharmaceuticals and personal care products，PPCPs）已經是達到隨處可得的地步，雖然改善了許多生活上以及疾病等的問題，卻衍生了一些新的問題。過去文獻指出PPCPs能藉由許多不同的途徑進入到環境之中，其中最主要的途徑普遍被認為是廢污水處理系統的放流水，雖然PPCPs可以藉由廢污水處理系統中的生物處理進行生物降解或生物吸附來去除，但受制於藥品的物化特性，使得生物處理對於某些藥品的去除能力有限；這些不易被生物處理程序去除的PPCPs一旦進入消毒程序可能會與消毒劑反應形成對人體有害的消毒副產物(Disinfection byproduct，DBPs)，而其中具有二甲基官能基的PPCPs經過消毒程序後會反應生成具致癌性的亞硝胺類化合物(Nitrosamines)。
本研究選定三種常見之藥品包含作為抗癲癇藥物的卡馬西平(Carbamazepine）、屬於非類固醇消炎止痛藥(Non-Steroidal Anti-Inflammatory Drug，NSAID）的布洛芬(Ibuprofen）、以及具有鎮定及催眠效果的多西拉明(Doxylamine）作為研究對象，並透過(一)添加氧化石墨烯(Graphene oxide，GO)及藥品馴養污泥條件(命名為GSP）、(二)添加活性碳(Active carbon，AC)及藥品馴養污泥條件(命名為ASP）、(三)添加藥品馴養污泥條件(命名為SP）、(四)無額外添加馴養污泥條件(命名為S）四種馴養條件產出之厭氧污泥進行藥品去除批次實驗，以了解GO及AC的添加對於污泥去除藥品的能力影響，以及厭氧污泥是否經過藥品馴養對於去除藥品的能力上的差異；除了觀察藥品去除率以外，本研究亦希冀藉由量測亞硝胺生成潛勢來了解三種藥品經過不同馴養條件的厭氧污泥處理後放流水體中亞硝胺類化合物生成潛勢之變化影響，包含亞硝基二甲胺(N-Nitroso-dimethylamine，NDMA）、亞硝基甲基乙基胺(N-Nitrosomethylethylamine，NMEA）、亞硝基吡咯烷(N-Nitrosopyrrolidine，NPyr）、亞硝基二乙胺(N-Nitroso-diethylamine， NDEA）、亞硝基哌啶(N-Nitrosopiperidine，NPip）、亞硝基嗎啉(N-Nitrosomorpholine，NMor）、亞硝基二正丙胺(N-Nitroso-di-n-propylamine，NDPA）、亞硝基二正丁胺(N-Nitrosodi-n-butylamine ，NDBA）；除了針對二級厭氧處理外，本研究也將藉由模擬一般廢污水廠消毒程序，藉由加氯(次氯酸）消毒前述不同馴養污泥處理後之放流水，分析三種藥品若經過實廠厭氧生物處理後消毒的亞硝胺類化合物生成量。
結果顯示，GO的添加能夠促進厭氧生物的成長，並且因本身能夠幫助氧化還原反應的電子傳遞，在去除布洛芬的能力有一定能力的幫助，但同時也促進了亞硝胺類化合物的生成。水中的卡馬西平衍生物及其他代謝物會進行反應合成卡馬西平，使卡馬西平殘留濃度高於原始添加濃度，但活性碳的存在能減緩這種現象發生。
在去除藥品的批次實驗結束後進行加氯(次氯酸）消毒及生成潛勢的亞硝胺生成量結果中，因本身水樣的複雜性較高，含有的亞硝胺前軀物種類較多，但由於生成潛勢單純為氯胺生成途徑，與加氯消毒同時所涉及到的氯-亞硝化反應和氯胺生成途徑不同，導致兩實驗的亞硝胺生成物種及生成量不同。生成潛勢之結果中，亞硝胺生成最高的物種以及實驗組合為GSP組污泥經六天接觸反應時間生物處理後NMor生成2434.94 ng/L，而加氯消毒實驗則是GSP經六天接觸反應時間生物處理後NDMA生成1437205.83 ng/L。

It has been shown in early studies that pharmaceuticals and personal care products (PPCPs) are released into the environment by multiple pathways. Effluents of domestic wastewater treatment plants (WWTPs) is known as the major contributor. As biological treatment is one important step in domestic wastewater treatment, PPCP removals by biological treatment are typically limited. Formation of carcinogenic disinfection byproducts (DBPs) is another concern during treatment of pharmaceutical-containing wastewaters. In this study, four anaerobic sludge incubation conditions (anaerobic sludge with graphene oxide (GO) and PPCPs; anaerobic sludge with active carbon (AC) and PPCPs; anaerobic sludge with PPCPs; and anaerobic sludge only) were developed and the effects of different incubation conditions on the PPCP removals were investigated. PPCPs of concern included carbamazepine (CBZ), ibuprofen (IBF) and doxylamine (DOX). In these incubation experiments, the formation potentials of eight nitrosamines (Nitrosamine-FPs), which are carcinogenic DBPs of pharmaceuticals and included N-nitroso-dimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosopyrrolidine (NPyr), N-nitroso-diethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitrosomorpholine (NMor), N-nitroso-di-n-propylamine (NDPA), N-nitrosodi-n-butylamine (NDBA) were also analyzed. In the results, adding GO facilitated the growth of anaerobic sludge. GO helped the removal of IBF but also elevated the nitrosamine-FPs. The byproducts and metabolites of CBZ could react to form CBZ in the wastewaters. The presence of active carbon appeared to reduce the reaction rate. Because of the complexity in the compositions of wastewater, several nitrosamine concentrations and nitrosamine-FPs increased after chlorination. Different pathways were involved when three pharmaceuticals reacted during biological treatment or with chlorine during post-chlorination after biological treatment. Chloramination was the more important mechanism for nitrosamine-FPs variations during biological treatment, whereas chlorine-enhanced nitrosation and chloramination were both critical for nitrosamine concentrations during post-chlorination after biological treatment. This study provided insight into the effect of adding a novel GO material during anaerobic biological treatment on the removals of pharmaceuticals in wastewaters, which is an increasingly important concern for sustainable development of wastewater treatment technologies.

摘要 i
目錄 v
圖目錄 viii
表目錄 xi
第一章 前言 1
1.1　研究緣起 1
1.2　研究目的 3
1.3　研究架構 5
第二章 文獻回顧 7
2.1 藥品及個人保健用品 7
2.1.1 藥品及個人保健用品之流佈 8
2.1.2 藥品及個人保健用品之危害 9
2.1.3 藥品及個人保健用品之去除方法 10
2.2 厭氧生物處理 11
2.3 消毒副產物 13
2.4 亞硝胺類化合物 14
2.4.1亞硝胺類化合物生成機制 16
2.4.2 亞硝胺類化合物毒理反應 20
2.4.3 亞硝胺類化合物之法規規範 21
2.5 氧化石墨烯 22
第三章 實驗材料與方法 23
3.1 實驗藥品與儀器設備 23
3.1.1 實驗藥品 23
3.1.2 實驗設備與儀器 28
3.1.3 消毒劑次氯酸及一氯胺之配製 29
3.2 實驗研究 30
3.2.1 厭氧污泥馴養之SBR試驗 30
3.2.2 不同馴養方式產出之污泥測試去除藥品批次實驗 31
3.2.3 不同馴養方式產出之污泥測試去除生成潛勢之批次實驗 32
3.2.4 污泥批次實驗後加氯(次氯酸）消毒程之亞硝胺生成實驗 32
3.3 實驗樣品分析 33
3.3.1 藥品類樣品前處理 33
3.3.2 亞硝胺類化合物樣品前處理 34
3.3.3 藥品分析 34
3.3.4 亞硝胺類化合物分析 36
3.3.5 自由餘氯分析 38
3.4 實驗室品質保證與品質管理 39
3.4.1 儀器分析檢量線 39
3.4.2 方法偵測極限 39
第四章 結果與討論 40
4.1 以SBR進行不同條件厭氧污泥之馴養 40
4.1.1 MLSS及MLVSS之濃度變化 41
4.1.2 COD之去除效果 43
4.2 不同馴養條件產出之厭氧污泥進行模擬處理之批次實驗 45
4.2.1 MLSS及MLVSS濃度變化 45
4.2.2 氨氮、硝酸鹽氮、亞硝酸鹽氮濃度變化 49
4.2.3 水體中DOC、UV254以及SUVA值濃度變化 52
4.3 不同馴養條件產出污泥批次實驗之藥品去除能力 55
4.3.1 不同馴養條件產出污泥在各接觸時間批次實驗藥品去除能力 55
4.3.2各接觸反應時間下不同馴養條件產出污泥處理藥品之殘留量 58
4.4 批次實驗產出水樣之亞硝胺生成潛勢 63
4.4.1 各亞硝胺在不同接觸反應時間之生成潛勢濃度變化 63
4.4.2 各水力停留時間下亞硝胺類化合物生成潛勢之變化 66
4.5 批次實驗後加氯(次氯酸)消毒程序之亞硝胺生成濃度 71
4.5.1亞硝胺化合物經不同接觸反應時間之加氯消毒生成濃度變化 71
4.5.2 各接觸反應時間下加氯消毒程序亞硝胺類化合物生成量變化 75
4.6 結果總結 79
第五章 結論與建議 79
5.1 結論 80
5.2 建議 82
參考文獻 84

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王雅虹 (2016)藥品及個人保健用品經加氯氧化程序生成新興消毒副產物亞硝胺之研究