1.食品清潔劑中烷基酚類化合物之含量調查與殘留分析 2.利用固相微萃取與衍生技術檢測水中之烷基酚類化合物

Abstract

Part.1 所謂食品用清潔劑係指直接使用於清潔食品、食品器具、食品容器及食品包裝之物質，在現代的日常生活中被廣泛地使用。清潔劑之主要成份為界面活性劑，而烷基酚類化合物因為具有良好之洗淨力，因此為界面活性劑的主要原料；然而，由於此類化合物結構與天然雌性激素相似，進入人體後會呈現類動情激素的作用，而其流佈於環境中亦具有降解不易、造成生態衝擊等問題，因此有部分國家已對於該類化合物之使用進行管制。為了評估烷基酚類化合物對國人健康的潛在危害程度，本研究針對暴露風險較高的食品用清潔劑，分析市售產品中烷基酚類化合物的含量，包括：辛基苯酚(4-t-octylphenol；4-t-OP)、壬基苯酚(4-nonylphenol； 4-NP)、及含有異構物之壬基苯酚(t-NPs；technical nonylphenol isomers)等，並藉由殘留分析試驗的結果，推估人體暴露之平均每日攝取劑量。 研究針對75件市售食品用清潔劑調查的結果發現，食品清潔劑中壬基苯酚類化合物之濃度範圍為1.71E-06至2.13E-04% (烷基酚類化合物g/清潔劑g)；且4-t-OP、4-NP及t-NPs等在食品用清潔劑中之含量及被檢出率，皆以t-NPs為最高。 殘留分析部份，利用田口式實驗設計(Taguchi Experimental Design)，探討食品用清潔劑使用後烷基酚類化合物的殘留問題，結果發現：1)餐具部份，辛基苯酚(4-t-OP)之殘留受到清潔劑清洗溫度因素的影響，壬基苯酚(t-NPs)之殘留則是受到清洗後再次使用時水溫的影響；2)蔬果部份，包括蔬果種類、界面活性劑濃度、烷基酚類化合物添加濃度，均有可能會影響蔬果清洗後t-NPs的殘留量。另一方面，本研究結合了含量調查與殘留分析之數據與其他相關資料，進行了經由飲食之初步攝取劑量估計；然而，除了因使用而造成的殘留問題之外，其他在環境中之暴露量(例如因降解而產生之短鏈壬基苯酚等)，亦有必要再進一步研究其可能來源，以進行更完整的暴露評估。 Part.2 烷基酚類化合物 (Alkylphenols；APs) 大量用於製造烷基苯酚聚乙氧基醇類界面活性劑，並是許多產業製程的原料；然而由於此類化合物結構與天然雌性激素相似、進入生物體後會呈現類動情激素的作用，而其流佈於環境中降解不易，會造成生態衝擊等之問題，因此有部分國家已對於該類化合物之使用進行管制。為了瞭解烷基酚類化合物對環境及人體健康的可能影響，本研究嘗試結合固相微萃取 (solid-phase microextraction；SPME)與衍生技術，搭配氣相層析質譜儀，發展可同步檢測水中烷基酚類化合物 (包括：辛基苯酚 4-t-OP、壬基苯酚 4-NP、及含有異構物之壬基苯酚 t-NPs) 含量的方法，以改進現有偵測水中APs的缺點。研究中首先以SPME頂空萃取水中之烷基酚類化合物，再將吸附APs之纖維，以頂空方式與含有1% tert-Butyldimethylchlorosilane (TBDMCS)之衍生試劑N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) 在纖維上進行衍生反應。 本研究所探討影響SPME與衍生的條件包括: 纖維裹覆的材質、萃取的時間與溫度、鹽類的添加、轉速的設定、衍生的時間與溫度、及熱脫附的條件等。研究結果顯示，85µm polyacrylate 的纖維對於APs與其衍生物有最佳的吸附效率；此外，30分鐘65℃的萃取以及10分鐘45℃的衍生為最適的SPME與衍生條件。在此最佳化條件下，4-t-OP、t-NPs、及4-NP之線性範圍分別為0.005–1.04 μg/L、 0.005–1.00 μg/L、及0.005–0.43 μg/L；方法偵測極限介於1.58–3.85 ng/L。與不進行衍生反應之SPME方法比較，除了4-t-OP以外，經由衍生技術的方法均有較好的線性關係、方法偵測極限、相對標準差與回收率。與其他方法比較，本研究除了可提供更佳的敏感度外，並且可減少複雜的分析程序與操作時間。

Part 1 Household food detergents are widely used for dish washing and fruit cleaning in modern daily life. As for the ingredients of synthetic food detergents, the non-ionic surfactants are mostly composed of alkylphenols. Due to the ability to mimic hormones, it has been noticed that the exposures of alkyllphenols might cause a variety of adverse effects. Therefore, the purpose of this research was to determine the concentrations of alkylphenols in food detergents and also to perform the residual analysis after their use. Alkylphenols including 4-nonylphenol (4-NP), technical nonylphenol isomers (t-NPS), and 4-tert-octylphenol (4-t-OP) were target compounds of this research because of the possible health risks they might cause. The samples of the detergents were analyzed by GC/MS after dilution. The Taguchi experimental design was utilized to study the main factors that might affect the residual characteristics after the using of detergents. The results showed that the concentrations of alkyllphenols in food detergents, including 4-NP, t-NPs and 4-t-OP, ranged from 1.71E-06 to 2.13E-04% (APs g/detergent g) in 75 samples. Among the alkylphenols investigated, both the detectable rate (66.67%) and the concentration (0.000213%) were the highest for t-NPs. The results also showed that cleaning temperature will affect the residual of 4-t-OP while sampling temperature will affect the left of t-NPs on dishware. On the other hand, the varieties of fruits, the concentrations of detergents, and the concentrations of alkylphenols were also found to have significant effects for the residuals of t-NPs on food. As for the assessment of human exposures, the research combined the results of residual analysis and other relative data to evaluate the average daily intakes dose from food ingestion. However, exposures from other sources are needed to assess the whole exposures of alkylphenols for the general population in Taiwan. Part 2 Alkylphenols (APs) was man–made chemicals which are used as the major components of non-ionic surfactants and are important to a number of industrial processes. Due to the property to mimic hormones, it has been noticed that the APs can cause a variety of adverse effects in ecology. Many researches have reported on the wide occurrence of APs in the environment matrices. The notice of the presence of APs in the environment has led to an increased interest in the trace analysis of these compounds. Therefore, the purpose of this research was to develop a method for the simultaneous analysis of APs (4-tert-octylphenol; 4-t-OP, technical nonylphenol isomers; t-NPs and 4-nonylphenol; 4-NP) in water which will be simple, fast and reliable. A two-step sample preparation procedure, including headspace extraction of APs in water first followed by the on-fiber derivatization with N-tert-Butyl- dimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) with 1% tert-Butyl- dimethylchlorosilane (TBDMCS), was established. The 85μm polyacrylate (PA) fiber was selected and headspace extraction of APs in water for 30 minutes at 65℃ was first performed followed by the on-fiber derivatization with MTBSTFA for 10 minutes at 45℃. The analytical method was linear over the ranges of 0.005–1.04, 0.005–1.00, and 0.005–0.43μg/L for 4-t-OP, t-NPs and 4-NP, respectively while the method detection limits (MDLs) were in the range of 1.58–3.85 ng/L. Compared with other technique, the proposed method provided a simple, fast and reliable method for the analysis of APs in water.