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博碩士論文 etd-0109115-223925 詳細資訊
Title page for etd-0109115-223925
論文名稱
Title
新興污染物於台灣河川水體與海洋環境中殘留量分布及來源特性探討之研究
Characterizing the behavior and source contribution of emerging contaminants in the riverine and marine environment across 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
149
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
2015-01-26
繳交日期
Date of Submission
2015-02-10
關鍵字
Keywords
受體模式、來源鑑識、毒品禁藥、藥物、新興污染物
emerging contaminants, pharmaceuticals, illicit drugs, source apportionment, receptor model
統計
Statistics
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The thesis/dissertation has been browsed 5791 times, has been downloaded 51 times.
中文摘要
新興污染物如藥物、個人保健用品及毒品禁藥近年來已經被發現會殘留於水體環境中,並且進一步會對人體造成威脅與影響。因此,這類新興污染物於台灣地區的河川水體與海洋環境的研究與規範仍然迫切的需要。故本論文的第一部分,首先針對台灣西南近岸海域,調查新興污染物於海水中的殘留分布、來源探討與風險評估。研究結果發現13種新興污染物被偵測到,中值濃度範圍從1.47 ng/L至156 ng/L。新興污染物空間分布的結果進而指出這類污染物主要透過河川的直接輸入與污水處理廠污水放流管的排放,最終進入海洋環境中。Codeine與ampicillin兩種化合物則發現風險商數超過1,顯示對水體生物可能造成影響。此外,針對墾丁地區一年一度所舉辦的春天吶喊音樂季期間,探討新興污染物的時空分布情形與遊客所帶來之影響與衝擊。採樣策略設計為針對淡季與旺季,以及春天吶喊前後與春天吶喊期間,藉以探討新興污染物的特徵變化。結果顯示出新興污染物濃度於春天吶喊期間最高,而相對的淡季則最低。主成分分析與春吶期間的組成特徵可以進一步評估因遊客所帶來之影響與衝擊。我們也發現ketamine與MDMA此類毒品禁藥於春吶期間所造成較高的環境負荷量,間接提供這類毒品使用與消耗之證據。
同時,我們利用多變量統計分析結合受體模式,發展出一套方法:”Pharmaco-signature”,來針對大高雄地區不同河川流域來探討此區新興污染物之潛在來源貢獻與特性。透過結合群集分析方法與主成分分析配合複迴歸分析之方式,可以將不同地區中,評估與發掘其顯著的污染來源之貢獻量。研究結果顯示,大高雄地區中新興污染物的來源貢獻所佔的比例分別為生活污水(58.9%)、抗生素之使用與應用(9.7%)、及禁藥之使用(31.4%)。此外,為了應用所發展出的”Pharmaco-signature”概念,
我們分別於中台灣(台中)與南台灣(台南)針對兩個不同複合水系進行樣品採集與分析。研究結果可以成功推斷於南部水系中,生活污水來源貢獻比例達62.2%,抗生素的使用佔16.9%,而禁藥的使用比例為20.9%;中部水系方面,生活污水比例佔47.3%,抗生素的使用來源貢獻比例上升至35.1%,禁藥的使用比例佔17.6%。本研究後期透過使用”Pharmaco-signature”的概念,來協助判斷並特徵化在複雜的水體環境中新興污染物可能的來源特性與貢獻,期望提供更進一步的了解與知識。
Abstract
Pharmaceuticals and personal care products, and illicit drugs referred to as emerging contaminants (ECs) have recently been detected in the aquatic environment and may have adverse human healthy effects. A clear picture of EC contamination in the marine and riverine environment of Taiwan is needed to gain insight for research and regulatory needs (e.g. monitoring, control and management). In first part of this thesis, the sources, distribution, and risk presented by ECs in coastal waters off southwestern Taiwan were estimated. The median concentrations for the detected 13 ECs ranged from 1.47 ng/L to 156 ng/L. Spatial variation in concentration of the 13 ECs suggests discharge into coastal waters via ocean outfall pipes and rivers. Codeine and ampicillin have significant pollution risk quotients (RQ >1), indicating potentially high risk to aquatic organisms in coastal waters. In second part, the origin, temporal magnitudes, potential risks and mass inputs of ECs were investigated in the youth festival as we refer to Spring Scream, a large-scale pop music festival, which is notorious for the problems of drug abuse and addiction. Sampling strategy was designed to characterize EC behavior in different stages (before and after the youth festival), based on multivariate data analysis to explore the contributions of contaminants from normal condition to the youth festival. Seasonal variations were observed, with the highest concentrations in April (Spring Scream) and the lowest in October (off-season). Principal component analysis (PCA) and weekly patterns provide a perspective in assessing the touristic impacts and address the dramatic changes in visitor population and drug consumption. The highest mass loads discharged into the aquatic ecosystem corresponded to illicit drugs/controlled substances such as ketamine and MDMA, indicating the high consumption of ecstasy during Spring Scream.
On the other hand, this study developed a methodology based on multivariate data analysis for characterizing potential source contributions of ECs detected in 26 river water samples across multi-scape regions in Kaohsiung during dry and wet seasons. Based on this methodology, we unveil an approach toward potential source contributions of ECs, a concept we refer to as the “Pharmaco-signature.” Exploratory analysis of data points has been carried out by unsupervised pattern recognition (hierarchical cluster analysis, HCA) and receptor model (principal component analysis-multiple linear regression, PCA-MLR) in an attempt to demonstrate significant source contributions of ECs in different land-use zone. PCA-MLR identified that 58.9% of the mean summed ECs were contributed by domestic impact, 9.7% by antibiotics application, and 31.4% by drug abuse in Kaohsiung. Finally, to make an application to the pharmaco-signature on characterizing the source contributions of ECs in aquatic environments, we collected water samples from the water systems in two megacities. We could successfully infer that the source percentage contributions were 62.2% for domestic inputs, 16.9% for antibiotics application, and 20.9% for drug abuse/medication in southern water systems, while 47.3% of the mean summed ECs were contributed by domestic inputs, 35.1% by antibiotics application, and 17.6% by drug abuse/medication in central water systems. Therefore, the use of pharmaco-signature is able to give the first impression of the profile and source apportionment of ECs in complex water systems, which provided important information for environmental management.
目次 Table of Contents
論文審定書.……………………………………………………………………………i
致謝…………………………………………………………………………………….ii
摘要……………………………………………………………........................……..iv
Abstract………………………………………………………………………………..vi
Chapter 1 Introduction…………………………………………………………………1
Chapter 2 Emerging Organic Contaminants in Coastal Waters: Anthropogenic Impact, Environmental Release and Ecological Risk………………………………6
2.1 Introduction……………………………………….……………………...............6
2.2 Materials and methods……….…………………………………………………..8
2.2.1 Sample collection……….……………………………………………………...8
2.2.2 Chemicals and standards……….……………………………………………..9
2.2.3 Extraction and analytical procedure…………………………………………12
2.2.4 Detection, quantitation, and analytical quality controls…………………...15
2.2.5 Method performance…………………………………………………………..15
2.2.6 Calculation of predicted no-effect concentrations and risk assessment...16
2.3 Results and discussion……….…………………………………………………17
2.3.1 Occurrence of EOCs in coastal waters…………………………….……….17
2.3.2 Environmental distribution of EOCs…….…………………………………...21
2.3.3 Source apportionment of EOCs in coastal waters based on PCA…….…24
2.3.4 Environmental risk assessment for coastal waters………………………..26
Chapter 3 Impacts of Emerging Contaminants on Surrounding Aquatic Environment From a Youth Festival…..........................................................30
3.1 Introduction……………………………………….…………………………....…30
3.2 Materials and methods……….………………………………………………....33
3.2.1 Materials……….………………………………………………………...........33
3.2.2 Study area and sample collection ……….………………………………....33
3.2.3 Sample preparation and analysis ………………………………................35
3.2.4 Method performance ……………………....…………………….................36
3.2.5 Mass loads estimation …………………..............…………………………37
3.2.6 Multivariate statistical analysis …………………………………………......38
3.3 Results and discussion……….…………………………………………………39
3.3.1 Temporal and spatial variation…………………………….………………….39
3.3.2 Behavior and contribution from the youth festival…………………………..44
3.3.2.1 Weekly patterns……………………………………………………………..44
3.3.2.2 Principal component analysis……………………………………………...47
3.3.3 Mass loads…….……………………………………………………………....49
3.3.4 Environmental implications………………………….…….………………....51
Chapter 4 Source Apportionment and Risk Assessment of Emerging Contaminants: An Approach of Pharmaco-signature in Water Systems……………………………………………………………………………....52
4.1 Introduction……………………………………….………………………………52
4.2 Materials and methods……….…………………………………………………54
4.2.1 Materials ……….………………………………………………………………54
4.2.2 Study area and sample collection ……….………………………………….55
4.2.3 Sample preparation and analysis …………………………………………...58
4.2.4 Method validation and quality control ……………………………………….59
4.2.5 Environmental risk assessment ……………………………………………..62
4.2.6 Multivariate statistical analysis ……………………………………………...62
4.3 Results and discussion……….…………………………………………………64
4.3.1 Occurrence of ECs ………………………….………………………………..64
4.3.2 Patterns and signatures …….………………………………………………..70
4.3.3 Source contribution …………………………………………………………...73
4.3.4 Environmental risk characterization ………………………….…….……….81
4.4 Limitation, advantage and application ….……………………………………..82
Chapter 5 Source Contributions and Mass Fluxes for Chemicals of Emerging Concerns: A Chemometric Application of Pharmaco-signature in two Water Systems……………………………………………........................................…85
5.1 Introduction……………………………………….………………………………85
5.2 Materials and methods……….…………………………………………………87
5.2.1 Chemicals and standards.……………………………………….................87
5.2.2 Water systems and sample collection ……….…………………………….87
5.2.3 Analytical methods…………………………………………………………….89
5.2.4 Quality analysis and quality control…………………………………………91
5.2.5 Statistical analysis…………………………………………………………....92
5.3 Results and discussion……….…………………………………………………93
5.3.1 Occurrence and distribution of CECs …………….…………………………93
5.3.2 Mass fluxes of CECs.…………………………………………………….…..97
5.3.3 Pharmaco-signature and source contribution of CECs …….…...............99
5.3.3.1 Cluster analysis……………………………………………………….........99
5.3.3.2 PCA-MLR analysis ………………………………………………………..101
5.3.4 Ecotoxicological risks of CECs ……………………….…….……………..107
Chapter 6 Conclusions ……………………………...………………..................110
6.1 Occurrence of ECs in marine environment…………………………….…….110
6.2 Special event’s impacts…………………………………………………………….…….…………..111
6.3 Pharmaco-signature applications……………………………………………………………………….....113
References…………………………………………………..…….......................114
CURRICULUM VITAE……………………………………………………………....129
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