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

沈英宏(Shen Ying-Hung)

指導教授 ： 吳家誠

國立臺灣師範大學/理學院/化學系/博士(2015年)

https://doi.org/10.6345/NTNU202204861

摘要

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。

關鍵字

抗菌劑 ； 三氯沙 ； 三氯卡苯 ； 環境荷爾蒙 ； 固相微萃取

並列摘要

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.

並列關鍵字

Antibacterial Agents ； Triclosan ； Triclocarban ； Endocrine Disrupting Chemicals ； Solid Phase Micro-Extraction

參考文獻

1. MOE, Strategy Programs on Environmental Endocrine Disruptors（SPEED 98）, Japan, (1998).

2. Skakkebaek, N. E., E. Rajpert-De Meyts, and K. M. Main. "Testicular dysgenesis syndrome: an increasingly common developmental disorder with environmental aspects: Opinion." Human reproduction 16.5 (2001): 972-978.

3. Giesy, John P., et al. "Cell bioassays for detection of aryl hydrocarbon (AhR) and estrogen receptor (ER) mediated activity in environmental samples."Marine Pollution Bulletin 45.1 (2002): 3-16.

4. Eertmans, Frank, et al. "Endocrine disruptors: effects on male fertility and screening tools for their assessment." Toxicology in vitro 17.5 (2003): 515-524.

5. Osterlind, A. "Diverging trends in incidence and mortality of testicular cancer in Denmark, 1943-1982." British journal of cancer 53.4 (1986): 501.