以綠色化學概念檢測生物檢體中人工合成麝香與烷基酚類流佈之研究

Analysis of synthetic musks and occurence of alkylphenols in biota samples with green chemistry techniques

吳銘緯(Ming-wei Wu)

指導教授 ： 丁望賢

國立中央大學/理學院/化學系/碩士(2012年)

摘要

人工合成麝香在19世紀就已經拿來取代天然麝香，從起源最早的硝基麝香，到後來的多環、巨環與酯環麝香都被廣為使用，因價錢便宜及香味宜人，因此硝基麝香與多環麝香經常添加在個人護理產品中。隨著製造以及使用過程中的排放，導致這些人工合成麝香累積在水、底泥與魚體中，因此必須開發一套快速及便利方法來檢測魚體中麝香的殘留。
　　本研究第一部分是，利用一步完成的微波輔助頂空固相微萃取裝置搭配氣相層析質譜儀分析魚類樣品，方法不僅快速且只需少量溶劑便能使用。將魚肉與4 mL的甲醇混和並攪拌10分鐘，再添加13 mL的去離子水，以PDMS/DVB的塗覆纖維置樣品頂空後，使用80 W微波，萃取5分鐘。此方法的偵測極限為0.08 ng/g – 0.5 ng/g，定量極限為0.3 ng/g – 2 ng/g。
　　對於這些魚肉樣品的初步檢測結果顯示，大部分的樣品都能檢測到人工合成麝香，利用標準添加法進行定量分析，待測物的總濃度介於1.0至14.0 ng/g，而再現性的標準偏差範圍為0.4 %至9.8 %。本研究開發的微波輔助頂空固相微萃取搭配氣相層析質譜儀，是具有快速檢測，步驟簡便及穩定性佳的優點，克服傳統萃取法中耗時且需使用大量溶劑的缺點，可用來偵測環境中魚體內的人工合成麝香。

　　烷基酚為烷基酚聚乙氧基醇類非離子型界面活性劑在環境中所降解的產物，已被證實會干擾生物體的內分泌機制，被稱之為環境賀爾蒙。此化學物質有親酯性質，因此會累積於生物體中，本研究第二部分為檢測馬公、台西、布袋、東石、七股與箔子寮所採樣的螺種，以達到監測烷基酚在生物體中流佈研究。
　　本研究中，利用蒸氣蒸餾法搭配氣相層析質譜儀來檢測螺肉樣品，將螺肉樣品放入圓底瓶中，並且加入100 mL的去離子水混和，與含4 mL正己烷的蒸氣蒸餾管連接，萃取一個小時再使用1 μL衍生化試劑做線上衍生。定量極限皆於20 ng/g以下，每個待測物的回收率介於80.3 % - 114.9 %，而相對標準偏差範圍為2.4 % - 12.7 %。
　　環境中不同的4螺種(細紋玉螺、扁玉螺、蚵岩螺、象牙鳳螺)皆無檢測出4-t-OP，但都可以檢測出4-NPs，其濃度範圍為23 ng/g - 3370 ng/g，在本研究中，不同螺種、不同地區與不同時間所採集的螺種其4-NPs濃度皆有顯著差異性。

關鍵字

綠色化學 ； 麝香 ； 烷基酚

並列摘要

The use of musk flavor has a long history dating back to ancient times. Until the end of the nineteenth century the popular fragrance was obtained from natural sources. Nowadays synthetic compounds are almost exclusively used. They can be divided into four major classes: aromatic nitro musks, polycyclic musks, macrocyclic musks, and alicycloc musks. Due to their flavor odor and lower price, synthetic musks use to be added to personal care products, and release by the waste sludge and sewage. Musks also can easily accumulate in water, sludge, and biota, therefore a simple and effective method is required.
　　The first part of this study, one-step in situ microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) coupled with gas chromato- graphy-mass spectrometry (GC-MS) analysis was presented as a fast and eco-friendly technique to determine synthetic musks in fish samples. The fish sample mixed with 5 mL MeOH and 13 ml deionized water was efficiently extracted by a polymehtylsiloxane- divinylbenzene (PDMS/DVB) fiber place in the headspace when extraction was microwave irradiated at 80 W for 5 min. The limits of detection (LODs) ranged from 0.08 ng/g to 0.5 ng/g and the limits of quantification (LOQs) ranged from 0.3 ng/g to 2 ng/g.
　　A preliminary analysis of fish samples revealed that all sample can be detected the synthetic musks, using a standard addition method, musks concentration were determined to range from 1.0 to 14.0 ng/g with relative standard deviation (RSD) ranging from 0.4 % to 9.8 %.
　　The results show that this MA-HS-SPME and GC-SIM-MS are reliable, sensitive, and stable analytical technique for a trace determination of synthetic musks in fish.
　　4-tert-octylphenol (4-t-OP) and 4-nonylphenol isomers (4-NPs) are two persistent degradation products form widely used nonionic surfactants alkylphenol polyethoxylates (APEOs). They have been demonstrated to exhibit the ability to mimic natural hormones. The second part of this study is analysis and monitors the hydrophobic alkylphenol compounds in snail in Taiwan.
　　In this study, one-step steam-distillation extraction followed by a gas chromatography-mass spectrometry is presented as a simple technique to determine alkylphenols in snail samples. The snail sample mixed with 100 ml deionized water into 250 mL round bottle, and connected with steam distillation tube which contained 4 mL hexane, then extraction for one hour. The recovery for each samples range from 80.3 % to 114.9 % with RSD ranged from 2.4% to 12.7%.
　　The 4-NPs concentrations ranged from 23 ng/g to 3370 ng/g in 4 different species (Natica lineata, NL, Neverita didyma, Nd, Thais clavigera, TC, Babylonia areolata, BA), but 4-t-OP was not detected in snail samples. The results showed that the concentration of 4-NPs in snails were significant different among sampling locations, species, and years.

並列關鍵字

green chemistry ； musks ； alkylphenols

參考文獻

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