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博碩士論文 etd-0624118-150627 詳細資訊
Title page for etd-0624118-150627
論文名稱
Title
南台灣飲用水程序中亞硝胺生成潛勢與藥品之濃度變化暨多變量分析
Nitrosamine formation-potential and pharmaceutical concentration variations and multivariate analysis in major drinking water treatment plants of southern Taiwan
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
137
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2018-06-29
繳交日期
Date of Submission
2018-07-24
關鍵字
Keywords
加氯、藥品、生成潛勢、亞硝胺、臭氧、多變量分析、淨水處理
Pharmaceutical, Ozonation, Multivariate analysis, Chlorination, Nitrosamine, Drinking water
統計
Statistics
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The thesis/dissertation has been browsed 5656 times, has been downloaded 1 times.
中文摘要
飲用水消毒是二十世紀中最重要的公共衛生成就,至今卻也衍生出其它具致癌潛勢之新興消毒副產物如亞硝胺類化合物的生成,其中又以國際癌症研究機構歸類為2A致癌物種之二甲基亞硝胺(N–Nitrosodimethylamine,NDMA)最受關注。本研究選擇南台灣三座使用相同原水但不同處理策略(如前加氯或前臭氧)之淨水廠作為採樣地點,輔以多變量統計如主成分分析探討不同處理技術對八種亞硝胺生成潛勢之影響,並進一步確認環境因子之重要影響性,研究同時調查國內大量使用藥品二甲雙胍與雙氯芬酸為重要前驅物的可能性。

結果顯示,處理程序對改變亞硝胺生成潛勢之主要物種影響有限,主要以不同季節原水中有機物型態而改變,在枯水期(如冬季2017/1),三座廠址水中比UV吸光值(specific UV absorbance,SUVA)平均濃度為3 L/m-mg,水中有機物以小分子物種為主,三座淨水廠各處理程序亞硝胺生成潛勢皆以短鏈結構的NDMA為主要物種;在豐水期(如春季2017/4), SUVA平均濃度為6.7 L/m-mg,水中富含不飽和脂肪或芳香族有機物;亞硝胺主要物種則形成以環烷類之亞硝胺物種亞硝基吡咯烷(N-nitrosopyrrolidine,NPYR)、亞硝基嗎啉(N-Nitrosomorpholine,NMOR)、亞硝基哌啶(N-Nitrosopiperidine,NPIP)為主;二甲雙胍與雙氯芬酸存在濃度介於未偵測(ND)至800 ng/L,對於亞硝胺生成無明顯正相關,推測水體中可能含有其他對亞硝胺生成更重要的前驅物之存在。亞硝胺生成潛勢與各水質參數的關聯性與亞硝胺結構有關,趨勢上整體可分為:(a)短鏈脂肪族、(b)長鏈脂肪族、(c)環狀結構之亞硝胺,隨著亞硝胺分子量降低,多種水質參數對亞硝胺如NDMA之影響趨勢越相似,其中環烷類之亞硝胺物種可由SUVA、UV254作為良好的指標性參數(r值介於0.45~0.67)。

本研究希冀透過三座具比較性的淨水廠全年四季現場採樣與分析,了解亞硝胺生成潛勢與藥品污染環境宿命,找出重要關鍵因子以提供此類新興藥品污染物與衍生性有害副產物處理技術或防制策略之重要參考資訊。
Abstract
Although disinfection for drinking water is considered as one major achievement for public health in the 20th century, the formation of carcinogenic disinfection byproducts including the emerging nitrogenous nitrosamines is a concern. For example, N-nitrosodimethylamine (NDMA) classified in Group 2A by the International Agency for Research on Cancer (IARC) has arisen a widespread concern in the recent decades. Three drinking water treatment plants (DWTPs) in southern Taiwan that treat the same surface water source by using different but comparable treatment approaches (e.g., with pre-chlorination or pre-ozonation) were selected as sampling sites in this study. The objective was to investigate the fates of eight nitrosamine formation potentials (nitrosamine-FPs) among different technologies, with the assistance by analyses of typical water quality parameters and multivariate statistical analysis such as principal component analysis (PCA). In addition, two widely used pharmaceuticals in Taiwan including metformin and diclofenac were chosen as the possible precursors and studied for their potentials to form nitrosamines in these DWTPs. In the results, the occurrences of eight nitrosamine-FPs in three DWTPs mainly depended on the organic matter (OM) concentrtations in water, as the OM concentrations greatly varied among the sampling seasons. During the dry season (e.g., in winter), the average concentration of SUVA in the DWTPs was 3 L/m-mg and the nitrosamine-FPs were dominated by the compounds with small molecules that are more likely to form short-chain NDMA. During the wet season (e.g., in spring), the average concentration of SUVA in the DWTPs was 6.7 L/m-mg and the nitrosamine-FPs were dominated by unsaturated or aromatic compounds, which could form cycloalkane nitrosamines such as N-nitrosopyrrolidine (NPYR), N-nitrosomorpholine (NMOR), or N-nitrosopiperidine (NPIP). The concentrations of metformin and diclofenac ranged from non-detected (ND) to 800 ng/L. No significant correlation was observed between the pharmaceutical concentrations and nitrosamine-FPs, indicating the presences of other unknown precursors to form nitrosamines in the water. With the correlation analysis between the nitrosamine-FPs and typical water quality parameters, it was shown that the trends of nitrosamine formation in these DWTPs could be divided into: (a) short-chain aliphatic; (b) long-chain aliphatic; and (c) cyclic nitrosamines. With the decrease of the molecular weight, the nitrosamine-FPs such as NDMA-FP and NMEA-FP show similar trends of the correlations with typical water quality parameters. Additionally, the cyclic nitrosamine-FPs appeared to be predictable by certain parameters such as SUVA or UV254 (r = 0.45-0.67). The study aims to understand the environmental fates of eight nitrosamine-FPs and two pharmaceutical concentrations through four sampling seasons in a year. The findings are expected to provide insights into future management of these emerging pharmaceutical pollution and derivative byproducts.
目次 Table of Contents
論文審定書 i
摘要 ii
Abstract iv
目錄 vii
圖目錄 x
表目錄 xii
Nomenclature xiv
第一章 前言 1
1.1 研究緣起 1
1.2 研究問題 4
1.3 研究目的 5
第二章 文獻回顧 7
2.1 消毒副產物概述(Disinfection by-product,DBP) 8
2.1.1 含碳消毒副產物 11
2.1.2 新興含氮消毒副產物 13
2.2 亞硝胺類化合物(N-nitrosamine) 15
2.2.1 亞硝胺物化特性 15
2.2.2 亞硝胺毒理危害 18
2.2.3 亞硝胺管制標準 19
2.2.4 亞硝胺之流佈 24
2.3 亞硝胺生成機制 29
2.3.1 氯化生成機制(Chlorination) 30
2.3.2 氯胺化生成機制(Chloramination) 33
2.3.3 臭氧生成機制(Ozone) 35
2.3.4 活性碳生成機制(Activated Carbon,AC) 37
2.4 亞硝胺前驅物 38
2.4.1 胺類化合物(Amines) 38
2.4.2 藥品及個人保健(PPCPs) 41
2.5 藥品及個人保健之流佈 45
2.5.1 Metformin 48
2.5.2 Diclofenac 50
第三章 研究方法 53
3.1 研究架構與流程 53
3.2 場址選定與說明 55
3.3 實驗藥品與儀器設備 56
3.3.1 分析藥品 56
3.3.2 分析儀器與設備 58
3.4 實驗方法與設計 59
3.4.1 採樣與保存 59
3.4.2 水質項目與分析方法 60
3.4.3 藥品前處理 61
3.4.4 亞硝胺前處理 63
3.5 實驗室品質保證與品質管理(QA/QC) 65
3.5.1 偵測極限 65
3.6 資料分析 66
3.6.1 主成分分析 66
3.6.2 相關性分析 68
3.6.3 健康影響潛勢評估 69
第四章 結果與討論 73
4.1 本研究選定之各淨水處理程序間於不同採樣時間下水質背景變化 73
4.1.1 不同淨水單元間亞硝胺生成潛勢之分佈 73
4.2 不同淨水單元間藥品濃度變化 86
4.3 PCA分析影響八種亞硝胺生成潛勢之重要處理技術 91
4.4 亞硝胺生成潛勢與水質參數、藥品相關性分析 96
4.4.1 水質參數與亞硝胺生成潛勢間相關性分析 96
4.4.2 藥品與亞硝胺生成潛勢間相關性分析 101
4.5 健康影響潛勢評估 102
第五章 結論與建議 107
5.1 結論 107
5.2 建議 109
參考文獻 110
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