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研究生: 沈英宏
Shen, Ying-Hung
論文名稱: 環境中滅抑菌功能之環境荷爾蒙研究(三氯沙、三氯卡苯及其轉換產物)
A Study on Endocrine Disrupting Chemicals with Antimicrobial Activities in the Environment
指導教授: 吳家誠
Wu, Jia-Cheng
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2015
畢業學年度: 104
語文別: 中文
論文頁數: 162
中文關鍵詞: 抗菌劑三氯沙三氯卡苯環境荷爾蒙固相微萃取
英文關鍵詞: Antibacterial Agents, Triclosan, Triclocarban, Endocrine Disrupting Chemicals, Solid Phase Micro-Extraction
DOI URL: https://doi.org/10.6345/NTNU202204861
論文種類: 學術論文
相關次數: 點閱:124下載:12
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  • 三氯沙(Triclosan;TCS)和三氯卡苯(Triclocarban;TCC)是近年新發現具有環境荷爾蒙效應之常用的抗菌劑,且TCS和TCC及其衍生物MTCS、DCC、NCC及四氯卡苯(3,3’,4,4’ - tertachlorocarbanilide; 以下簡稱TetraCC)的共同存在於環境中。
    本研究使用自製介面串聯SPME(solid-phase-micro-extraction)與HPLC-DAD及HPLC-MS/MS,對此兩個新型的抗菌性內分泌干擾物質, TCS和TCC,及MTCS、NCC、DCC和TetraCC,在自來水、家庭飲用水、瓶裝水、和河川水中含量檢測建立了一套一小時內快速、綠色、靈敏的方法。研究中有關SPME的影響因子包含樣品氯化鈉濃度、pH值、萃取時間、脫附時間及樣本量等均進行SPME-HPLC-DAD及SPME-HPLC-MS/MS測試過取得最佳條件。由本研究結果可知此兩種檢測方法均有充足的感度、精密度和精確度其偵測濃度範圍可從水中ppt到pbb範圍。
    使用SPME-HPLC-DAD分析時,5mL樣本可達方法檢測限(MDL)0.060.21在去離子基質的水樣中和 0.120.73μg/L在河川水基質水樣中。SPME-HPLC-MS/MS時LOD更分別可達0.32-3.44ng/L (去離子水)和0.38-4.67ng/L(河川水),且基質添加準確度可達10%以內。且所有自來水的樣本中均測得TCS及TCC,可見TCS及TCC已經明顯汙染飲用水系統。平均而言,以70公斤成人為列,每天可能經由飲水攝入約170ng/day的TCC及200ng/day的TCS。可見TCS及TCC這類滅抑菌已經由飲用水威脅人們健康。因此,廢水處理和飲用水淨化流程應立即評估改進。

    Triclosan (TCS) and triclocarban (TCC) are recently discovered EDCs as commonly used antibacterial agents. The co-exist of TCS, TCC and their transformation products, methyl triclosan(MTCS), Carbanilide(NCC), 4,4’-dichloro- carbanilide (DCC) and 3,3’,4,4’ – tertachlorocarbanilide(TetraCC), in the environment.
    The presence of TCS and TCC, two endocrine-disrupting chemicals and antimicrobial agents, and transformation products of triclocarban, NCC, DCC and TetraCC, in tap water, treated household drinking water, bottled water, and river water samples were investigated using solid phase micro-extraction(SPME) on-line with HPLC-DAD or HPLC-MS/MS using a homemade interface, a rapid(< 1hour), green and sensitive method. Factors influencing the quantity of the analytes extracted onto the solid phase micro-extraction fiber, such as addition of salt, sample pH, extraction time, desorption time and sample volume, were optimized using SPME-HPLC-DAD and SPME-HPLC-MS/MS. The results showed that the method gave satisfactory sensitivities and precisions for analyzing sub-part-per-trillion levels of triclosan, triclocarban, and transformation products of MTCS, NCC, DCC and TetraCC in samples collected locally.
    Using SPME-HPLC-DAD, the method detection limit (MDL) of target compounds in 5 mL sample volumes spiked with analytes was as low as 0.060.21 μg/L for deionized water samples, and 0.120.73 μg/L for river water samples. Limits of detection were in the range of 0.32-3.44 ng/L and 0.38-4.67 ng/L for deionized water and river water samples, respectively using SPME-HPLC-MS/MS. Recoveries for spiked samples were in the range of 10%.
    Due to the results of this study, all the analytes were discovered in the tap water samples. Apparently, TCS and TCC are becoming popular contaminants in drinking water supplies. On average, the daily consumption of TCS and TCC by an adult by consuming 2 liters of different types of drinking water were estimated to be 170ng/day of TCC and 200ng/day of TCS. It is believed that the exposure to the antimicrobial agents TCS and TCC and transformation products of TCC in drinking water poses potential risks to human health. Wastewater treatments and drinking water purification processes can be evaluated and improved to prevent possible deterioration of pollution.

    中文摘要 I AbstractII 目錄 IIV 表目錄 VII 圖目錄 IIX 1第一章緒論 1 1.1研究動機與目的 1 1.2各國環境荷爾蒙管理與比較 6 1.2.1聯合國管理現況 6 1.2.2美國管理現況 8 1.2.3日本管理現況 13 1.2.4歐盟管理現況 23 1.2.5台灣管理現況 24 1.3環境荷爾蒙事件 42 1.4研究目標物之物理、化學性質及用途 48 1.4.1三氯沙及其轉換產物 48 1.4.2三氯卡班及其轉換產物 53 1.5環境中的流佈與毒性 55 1.6TCS、TCC及其轉換產物之分析技術探討 62 1.7固相微萃取(SPME) 64 1.7.1SPME 裝置 64 1.7.2SPME 原理 69 1.7.3SPME影響萃取效率參數 70 1.8光二極體陣列偵測器(Diode Array Detector) 75 1.9串聯式質譜儀 76 1.10研究架構 81 第二章實驗內容 83 2.1實驗儀器與設備 83 2.1.1採樣與前處理部份 83 2.1.2分析部份 84 2.1.3藥品、試劑及氣體 85 2.2實驗部分 87 2.2.1DAD分析標準品製備 87 2.2.2串聯質譜分析標準品製備 88 2.3玻璃器材之清洗 89 2.4SPME與HPLC串聯介面 90 2.5分析儀器條件的建立 91 2.6品質控制與管制 93 2.7方法準確度與精密度 96 2.8標準溶液滯留時間及其再現性與檢量線的建立 97 2.9偵測極限 (Detection Limit, DL) 測定 99 2.10檢量線確認及直接添加分析 100 2.11真實樣品的採樣及分析 100 第三章 結果與討論 105 3.1自製SPME與HPLC串聯介面 105 3.2SPME條件最佳化 106 3.2.1樣品pH、混合及氯化鈉濃度 106 3.2.2萃取時間、樣品體積及脫附時間 109 3.3儀器分析 112 3.3.1 SPME-HPLC-DAD 112 3.3.2 SPME-HPLC-MS/MS 112 3.4方法驗證 115 3.4.1 SPME-HPLC-DAD 115 3.4.2 SPME-HPLC-MS/MS 116 3.4.3方法結果研究比較 120 3.5真實樣品分析 123 3.6日常飲水攝取評估 125 3.7河川水樣分析調查 126 第四章 結論與建議 141 第五章 參考資料 145

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