淨水程序中數種環境荷爾蒙之監測

Identification of EDCs in drinking water treatment

陳家振(Jia-Jhen Chen)

指導教授 ： 李篤中

國立臺灣大學/工學院/化學工程學研究所/碩士(2009年)

https://doi.org/10.6342/NTU.2009.01935

摘要

現今，在環境荷爾蒙的檢測上，主要以氣相層析或液相層析質譜儀(GC、LC/MS)，但這類儀器的建構維護成本高，且實驗技術性高，不利於淨水程序上環境荷爾蒙之監測，故發展快速有效的濃縮並檢測水樣的方法本篇將討論的重點。
固相萃取法為現今在環境荷爾蒙上常用的濃縮法，本論文將探討影響天然動情激素固相萃取回收率的因素;酵素免疫分析法(ELISA/EIA)，是一種快速可靠的檢測法，本實驗中將比較兩種文獻上常用檢測天然動情激素的酵素免疫分析試劑, Cayman kit 及wako kit;高效能液相層析儀(HPLC)，其建構成本較質譜以低，且準確以也高，在本篇中將以HPLC連接紫外光源( UV )偵測進壬基酚及雙酚A的定性及定量實驗。環境荷爾蒙類物質對螢光及紫外光均有吸收，在本實驗中將進行天然動情激素、雙酚A及壬基酚對紫外光(UV)及螢光激發與吸收(EEM)光譜進行吸收之比較，探討最佳的偵測光源。最後利用上述系統對長興直潭兩廠各程序水進行進行壬基酚、雙酚A、天然動情激素及睪固酮之檢測。
實驗結果發現，在 固相萃取中，以DMSO溶劑做稀驟的回收率(81%)高於甲醇做稀釋之回收率(71%);濃縮倍率從5000倍升至50000倍，回收率從106.1%會降至56.43%。而在固相萃取的程序上 RJ Wong (2008)的程序回收率(91.7)，優於一般文獻上所使用的程序之回收率(78.03%)。在比較兩種檢驗天然動情激素之酵素免疫分析試劑上，結果發現，Cayman Kit效果其偵測極限、檢量線範圍(20ng~1700ng/L)明顯優於Wako Kit ( 32600 ng/L ~ 439000 ng/L)；在HPLC偵測壬基酚及雙酚Ａ上，兩者上均有良好的線性關系(Rsqure皆大於0.995)。壬基酚及雙酚A的最低偵極限( Limit of detection, LOD )分別為0.68ppm、0.15ppm。偵測光源的比較上，無論準確性上、敏感度上，螢光(ppb級，Rsquare>0.995)均優於紫外光(ppm級，Rsaqure>0.8)。
真實水樣的檢測上，直潭長興兩廠各程序水之天然動情激素及睪固酮的含量，其含量範圍介於未檢出~9ng/L。壬基酚及雙酚A之含量介於末檢出至0.5ppb。

關鍵字

環境荷爾蒙 ； 天然動情激素 ； 睪固酮 ； 雙酚A ； 壬基酚

並列摘要

This thesis focus on solid-phase extraction (SPE) and two detection methods of Endocrine Disrupting Chemicals (EDCs), i.e. enzyme -linked immunosorbent assay (ELISA/EIA) and high-performanceliquid chromatography (HPLC), in water treatment processes.
The ELISA / EIA is a fast and reliable detection method. Comparison of two commercial estradiol ELISA kits, i.e. ‘Cayman’ and ‘wako’, are made in this study. The results show that the detection limit and accuracy of Cayman Kit is better than Wako Kit.
The HPLC connected ultra-violet light (HPLC-UV) is used to qualitatively and quantitatively detect nonylphenol and bisphenol A in various unit process of water treatment plants. Both chemicals achieve good linear relationships (R square value are both higher than 0.995). The limit of detection (LOD) of Nonylphenol and bisphenol A are determined as 0.68ppm and 0.15ppm.
In order to determine the best light source of detecting estradiol, bisphenol A and nonylphenol, the HPLC-UV and fluorescence excitation and absorption (EEM) are used to compare their absorption spectras. The results indicate that EEM is significantly better than the UV light source (ppm level, R saqure value more than 0.8) in terms of accuracy and the sensitivity (ppb level, R square value more than 0.995).
SPE method is a common method for concentration trace target analysts. The concentration ratio, types of organic solvents and effects of various extraction steps of on the recovery of (estradiol, bisphenol A and nonylphenol) are addressed. In the organic solvent comparison, DMSO shows better recovery (81%) than methanol (71%). At the high concentration ratios, the concentration ratio increase from 5000~50000 times and the recovery rate decrease from 106.1% to 56.43%. In the comparison of SPE procedures, recovery 91.7% obtained in previous protocol (RJ Wong, 2008) are experimentally verified higher than those in the other literature (78.03%).
With regard to natural water analysis of all process units in two water treatment plants (Changhsing and Jhihtan WTP), the analysis ranges of natural estrogen and testosterone are from not detected (ND) to 9ng•L-1. water are detected in the range between ND to 0.5ppb.

並列關鍵字

EDCs, Endocrine Disrupting Chemicals ； estradiol ； ELISA ； nonylphenol

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