鄰苯二甲酸酯類 (phthalate esters, PAEs)係一群廣泛使用之塑化劑，由於鄰苯二甲酸酯類與塑膠材料並非以共價鍵結方式結合，因此易經由食物與包裝材料接觸後導致PAEs溶出進而污染食品。過去研究顯示，鄰苯二甲酸酯類對於動物及人類生殖、生長發育及肝臟具潛在之健康危害，因此，各國陸續擬訂法規以管制鄰苯二甲酸酯類的使用。對一般大眾而言，鄰苯二甲酸酯類的主要暴露源自於每日攝入的食品，因此了解各類食品中鄰苯二甲酸酯類背景含量是重要的。然而，截至2011年為止國內尚未有完整之食品中鄰苯二甲酸酯類背景值調查數據，以供評估國人經由飲食暴露鄰苯二甲酸酯類的健康風險。因此，須有合適的前處理及分析方法，俾利進行全面性的市售食物樣本分析。本研究之目的為開發四大類食物樣本 (嬰幼兒食品、飲料乳品類、油脂類、保健食品)之前處理及分析方法，以精確檢測四大類食物中所含9種鄰苯二甲酸酯類 (DMP、DEP、DIBP、BBP、DBP、DEHP、DnOP、DINP及DIDP)之背景含量，並據以進行國人攝食暴露劑量及健康風險評估。本研究針對四大類食物樣本，依其基質區分三種 (低脂含量食品、高脂含量食品及乳類製品)分別開發有效的前處理及分析方法；同時建立系統性的採樣策略，以採集具代表性的食物樣本，並以開發完成之方法使用高效率液相層析儀-電灑式離子化-串聯式質譜儀 (high performance liquid chromatography electrospray ionization tandem mass spectrometry, HPLC-ESI-MS/MS)進行市售500件食物中鄰苯二甲酸酯類含量分析，並將此分析技術轉由美和科技大學完成700件食品中PAEs含量分析。為了使攝食風險評估更貼近真實狀況，在暴露劑量計算上，以總數1200件食物樣本中鄰苯二甲酸酯類濃度檢測結果進行推估，而國人 (包含各年齡層之男性及女性)之攝食量及體重參數則引用國家攝食資料庫數據。在健康風險計算上，則是以國人暴露劑量與每日耐受量 (Tolerable daily intake, TDI) 或參考劑量 (Reference dose, RfD) 進行個別鄰苯二甲酸酯類之危害商數 (Hazard Quotient, HQ) 計算，進一步將HQ加總後得一危害指標 (Hazard index, HI)。前處理方法測試結果顯示，低脂含量食品可使用甲醇進行萃取；而高脂含量食品如食用油、奶油等則改以正戊烷：甲醇 (1：4, v/v)進行萃取以提高回收率；至於乳品類、嬰幼兒奶粉則以正戊烷：丙酮 (1：1, v/v)及正戊烷進行萃取，三種前處理方法之分析結果皆符合本研究之品保品管規範。本方法開發後共完成500件市售食物樣本中9種鄰苯二甲酸酯類背景含量檢測，結果顯示嬰幼兒食品、飲料及膠囊錠狀粉狀食品均以DEHP檢出率最高，DINP次之；而在油脂類中則以DINP (92 %)檢出率較高，DEHP (80 %)次之。此外，在飲料、嬰幼兒食品、膠囊錠狀粉狀食品及油脂類中鄰苯二甲酸酯之平均濃度皆以DEHP為最高，分別為0.068 (ND-1.10) µg/g、0.116 (ND-2.40) µg/g、0.699 (ND-6.40) µg/g、5.50 (ND-235) µg/g。進一步以1200件食品中鄰苯二甲酸酯類濃度推估國人暴露劑量，結果顯示，在各年齡層中皆以DHEP和ΣDBP(i+n)並列最高，其次為DINP。在風險特徵描述中，ΣDBP(i+n)於P95th暴露劑量下，0-3歲男性和女性嬰幼兒分別佔TDI之97 %及84 %。針對PAEs造成生殖不良效應之風險進行計算，結果發現0-3歲嬰幼兒和4-6歲女童之P95th危害指標值 (HI)均大於1，而4-6歲男性孩童HI則為0.95；至於PAEs造成肝臟不良效應之風險，則所有年齡層P95th危害指標值皆小於1。此外，本研究估算經由飲食暴露PAEs對雌激素受體 (ERα)影響之總和效應濃度，結果發現各年齡層中以4-6歲女童總和效應劑量最高 (9.36 μg/kg/day)，顯示4-6歲女童因PAEs暴露劑量較高，可能導致干擾ERα結合效應程度高於其他年齡層。由以上結果顯示因食用四大類食品而暴露鄰苯二甲酸酯類，可能對國人產生潛在之生殖危害疑慮，尤其針對學齡前孩童。建議未來除須持續針對四大類食品進行定期的監測外，亦應納入其他種類食品進行背景調查，以獲得完整的攝食劑量評估數據，維護食品安全及國民健康。

Phthalate esters (PAEs) are one of world’s most used groups of plasticizer. Those compounds are not covalent bonded to product and easily migrated into food by contacting with containers or packages. Numerous studies show that PAEs can cause adverse effect on human health, especially on the liver, reproduction and development. The major exposure route of PAEs for general population is via food ingestion. It is important to know what kinds and extent of food are contaminated with phthalates. Up to now, only limited results are available for the background levels of phthalates in Taiwanese food. In order to assess health risk for the general population related to PAEs exposure, the suitable extraction methods and comprehensive analysis for daily food are needed. Therefore, the aims of this study were : (1) to develop suitable pretreatment methods and validate four group foods (baby food, beverages and milk, oils and health supplement) for 9 phthalates (DMP, DEP, DIBP, BBP, DBP, DEHP, DnOP, DINP and DIDP) in 500 food products ; (2) to assess the daily intake of the Taiwan population for 9 phthalates ; (3) to conduct a cumulative risk assessment for daily dose of PAEs in different food items using the hazard index. Suitable extraction methods were developed for the three food matrices (low-fat products, high-fat products and dairy products). Representative samples of four group foods were purchased followed by systematic sampling strategy. The instrument analysis was performed by high performance liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). For the risk assessment, the phthalate concentration data resulted from the TFDA project (1200 food items) were used. We also estimated the daily dose of phthalates based on the food consumption rates and body weight by sex and age-specified population database from the Nutrition and Health Survey in Taiwan. In health risk, estimated daily dose were divided by TDIs or RfDs to produce Hazard Quotients (HQs), and Hazard Index (HI) can be defined as the sum of HQs. The developed extraction methods including (1) low fat content foods were extracted by methanol; (2) high fat content food were extracted by pentane : methanol (1:4, v/v); (3) dairy products were extracted by pentane : acetone (1:1, v/v) and pentane. All analytical result had met the regulation of quality assurance and quality control. In this survey, DEHP was the most dominant phthalate in three groups, followed by DINP; however, DINP (92 %) was the most abundant phthalate in oil groups, followed by DEHP (80 %). Moreover, DEHP was found the highest average concentration in beverages, baby food, health supplements and oil samples, namely 0.068 (ND-1.10) µg/g, 0.116 (ND-2.40) µg/g, 0.699 (ND-6.40) µg/g and 5.50 (ND-235) μg/g. The daily dose of 9 PAEs for the Taiwan population indicated that DEHP and ΣDBP(i+n) were the highest, followed by DINP. Those compounds posed the highest risk potential of all the phthalates. Besides, the 95th percentile of daily dose for ΣDBP(i+n) (including DnBP and DIBP) in male and female children (0-3 years) were equal to 97 % and 84 % of TDIs, respectively. Regarding to the reproductive effects of phthalates, the 95th percentile HIs in children (0-3 years) and girls (4-6 years) were greater than 1, and boys (4-6 years) reached almost 0.95(HI). For the adverse hepatic effects, the 95th percentile HIs in all the population were below 1. We also calculated the aggregated dose to estimate the internal estrogenic activities of PAEs due to the different ERα binding affinities of PAEs. We found that aggregated dose of 4-6 years girls was 9.36 μg/kg/day and higher than other groups. These results show that it is probably that Taiwan general population are suffering adverse health effects from four group foods exposure to these phthalates, especially preschool children. In the future, it is need to investigate continuously for four group foods; moreover, extent to other food groups. Future investigation need to focus on possible contamination routes for phthalates during foodstuff manufacturing (oil and health supplement).

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吳宜勳，水中鄰苯二甲酸酯類採樣分析方法之研究，國立清華大學碩士論文，民國九十三年。
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黃康帆，市售食品、食品容器及包裝材料所含鄰苯二甲酸酯類化合物之調查及轉移試驗。國立嘉義大學碩士論文，民國九十九年。