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研究生： 鍾尹如
Yin-Ju Jhong
論文名稱： 以質譜技術對環境中多溴聯苯醚檢測之方法開發與應用
Determination of Polybrominated diphenyl ethers (PBDEs) in environment samples by mass spectrometry-method development and applications
指導教授： 丁望賢
Wang-Hsien Ding
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
畢業學年度： 94
語文別： 中文
論文頁數： 132
中文關鍵詞： 大氣壓力光游離法 、加壓溶液萃取法 、多溴聯苯醚 、氣相層析質譜儀 、液相層析質譜儀
外文關鍵詞： Pressurized liquid extraction, Polybrominated diphenyl ethers, Gas chromatography, Atmospheric pressure photoionization, Liquid chromatography
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    • 多溴聯苯醚(Polybrominated diphenyl ethers, PBDEs)為廣泛使用的耐燃添加劑，應用於各種民生用品與建築材料。PBDEs具有低反應、低揮發性、高親脂性等性質，而被視為持久性環境污染物，在環境中多存在於底泥、生物檢體等固態樣品中。PBDEs結構相近於甲狀腺T4激素，而視為甲狀腺荷爾蒙干擾物，亦具有神經毒性與致癌可能性。PBDE為可能形成溴化戴奧辛與溴化呋喃的前驅物，因而為歐盟危害物質限用指令(Restriction of Hazardous Substance, RoHS)中明定禁用物之一。
    索氏萃取法(Soxhlet extraction)與液固萃取法(Liquid-solid extraction)等傳統萃取法具有損耗大量溶劑、冗長實驗時間及不易自動化等缺點，因此發展加壓溶液萃取法(Pressurized liquid extraction, PLE)對固態環境樣品中PBDEs做有效萃取。在添加PBDEs標準品的無污染高嶺土樣品中，利用改變溶劑組成、溫度、壓力與萃取時間等參數而得最佳化條件，可得最佳回收率為51.9%-103.6%，相對標準偏差值介於1.6%~19.2%之間。
    將所發展之最佳化加壓溶液萃取技術應用於不同地區的固態環境樣品，並搭配氣相層析質譜技術作為偵測，建立穩定且堅固的定性定量之分析步驟，檢測多溴聯苯醚的濃度，可得偵測極限範圍為0.1~100 ng/g；定量極限範圍為0.5~200 ng/g。檢測台灣地區七處採樣點的底泥發現，皆有多溴聯苯醚污染，檢出率高達100%；檢出物種包含三溴聯苯醚BDE-028，四溴聯苯醚BDE-047、BDE-085，五溴聯苯醚BDE-099、BDE-100，六溴聯苯醚BDE-138、BDE-153、BDE-154，七溴聯苯醚BDE-183，八溴聯苯醚BDE-203，九溴聯苯醚BDE-206，與十溴聯苯醚BDE-209，各地PBDEs總濃度範圍為7990 pg/g ~37900 pg/g。單口蚓生物檢體亦受多溴聯苯醚污染，檢出物種包含三溴聯苯醚BDE-028，四溴聯苯醚BDE-047，五溴聯苯醚BDE-099、BDE-100，六溴聯苯醚BDE-153、BDE-154，七溴聯苯醚BDE-183，八溴聯苯醚BDE-203，九溴聯苯醚BDE-206，與十溴聯苯醚BDE-209，PBDEs總濃度為434000 pg/g。
    建立十溴聯苯醚於液相層析質譜儀(LC/MS)中最佳化層析與質譜游離化條件，以輔助定性與定量十溴聯苯醚於環境底泥樣品與生物檢體中濃度，為本研究另一目標。結果顯示，以甲醇:水溶液(99:1,v/v)作為動相組成溶液，以流速0.6 mL/min沖提並搭配5%異辛烷為摻雜劑進入大氣壓光游離源(APPI)，於毛細管電壓1600V、汽化溫度250℃與乾燥氣體溫度250℃最佳化條件下游離，以MS/MS模式分析，可得偵測極限為50 ng/g；定量極限為150 ng/g。且GC/MS與LC/MS/MS兩種方法用於檢測環境中十溴聯苯醚濃度在95%可信度下無明顯差異。

    Polybrominated diphenyl ethers (PBDEs) have multiple applications, either as an additive component or reactive. If use as an additive, PBDEs are not chemically bonded to the polymeric material and therefore may be released or leached from its surface into the environment. PBDEs act as hormone disruptors, neurodevelopmental toxics, and in some cases, carcinogenic agents. In addition, the combustion of these compounds could generate highly toxic polybrominated dibenzo-p- dioxins/furans.
    A time- and solvent-saving method, pressurized liquid extraction (PLE), to extract PBDEs in sediment was developed in this study. The effects of various operational parameters (i.e., temperature, pressure, etc.) for the quantitative extraction of PBDEs by PLE were investigated. The analytes were then identified and quantitated by GC-MS technique. The PBDEs can be completely extracted by CH2Cl2 : n-hexane (3:2, v/v) at 100?C and 100 atm combined with 15 min static and then 15 min dynamic extraction steps. Recovery of PBDEs in spiked blank kaolin samples ranged from 52 to 104% with 2-19% RSD. Comparison with Soxhlet method, compatible results were obtained by using PLE with much shorter extraction time and a small quantity of solvent consumed. Limits of quantitation (LOQ) were established between 0.5 to 200 ng/g in 10 g of sediment sample. The total contents of PBDEs ranged from 7990 to 37900 pg/g in various river sediments. Deca-BDE (BDE-209) was the major PBDEs detected in sediment samples.
    Additionally, LC-MS/MS with atmospheric pressure photoionization (APPI) was used for the analysis of deca-BDE as a complementary quantitation method. Various LC and MS parameters were evaluated to optimize the abundance of deca-BDE signal. The nebulizer pressure was optimized as 60 psi; the drying gas flow rate and drying gas temperature were optimized as 10 L/min and 250?C, respectively; and the capillary voltage was optimized at + 1100 V in negative ion mode. Under these conditions, deca-BDE underwent [M?Br+O]? and [M?Br+ O-2Br]? fragmentations. Isooctane was used as an effective dopant for indirect APPI analysis. Comparison with GC-MS method, compatible results were obtained by using LC-APPI-MS/MS with lower LOQ of deca-BDE (done to 150 ng/g in 10 g of sediment sample).

    目錄 中文摘要 -------------------------------------------------------------------- Ⅰ 英文摘要 -------------------------------------------------------------------- Ⅲ 謝誌 -------------------------------------------------------------------------- Ⅴ 目錄 -------------------------------------------------------------------------- Ⅵ 表目錄 ----------------------------------------------------------------------- Ⅷ 圖目錄 ----------------------------------------------------------------------- Ⅹ 第一章 緒論 --------------------------------------------------------------- 1 1-1 研究的緣起 ---------------------------------------------------------- 1 1-2 研究目標 ------------------------------------------------------------- 9 第二章 文獻回顧 -------------------------------------------------------- 11 2-1 耐燃劑 ---------------------------------------------------------------- 11 2-1-1 耐燃劑的簡介與原理 -------------------------------------- 11 2-1-2 耐燃劑之分類 ----------------------------------------------- 12 2-1-3 溴化耐燃劑簡介 -------------------------------------------- 14 2-2 多溴聯苯醚 ---------------------------------------------------------- 15 2-2-1 多溴聯苯醚簡介 -------------------------------------------- 15 2-2-2 多溴聯苯醚之性質 ----------------------------------------- 17 2-2-3多溴聯苯醚之毒性 ------------------------------------------ 19 2-2-4多溴聯苯醚之相關研究 ----------------------------------- 21 2-3 加壓溶液萃取法 ---------------------------------------------------- 27 2-3-1 加壓溶液萃取法之原理 ---------------------------------- 28 2-4 氣相層析質譜儀 --------------------------------------------------- 31 2-4-1 四極矩質譜儀 ---------------------------------------------- 32 2-4-2 選擇離子偵測法 ------------------------------------------- 33 2-5 液相層析質譜儀 ---------------------------------------------------- 35 2-5-1 大氣壓力光游離法 ----------------------------------------- 36 2-5-2 離子阱質譜儀 ----------------------------------------------- 40 第三章 實驗步驟與樣品分析 ---------------------------------------- 42 3-1 實驗藥品與儀器設備 ----------------------------------------------- 42 3-1-1實驗藥品 ------------------------------------------------------- 42 3-1-2 儀器設備 ------------------------------------------------------ 46 3-2 實驗步驟 -------------------------------------------------------------- 48 3-2-1 標準品的製備 ------------------------------------------------ 48 3-2-1.1 待側物標準品的製備 ------------------------------- 48 3-2-1.2 內標準品的製備 ------------------------------------- 48 3-2-1.3 擬似標準品的製備 ---------------------------------- 49 3-2-2 三至十溴聯苯醚同系物標準品之測定 ------------------ 49 3-2-3 十溴聯苯醚標準品之測定 --------------------------------- 52 3-2-4 加壓溶液萃取步驟 ------------------------------------------ 53 3-2-5 傳統索氏萃取步驟 ------------------------------------------ 54 3-2-6 真實樣品的萃取與淨化 ------------------------------------ 55 3-3 樣品採集 -------------------------------------------------------------- 57 3-3-1 採集方法 ------------------------------------------------------ 57 3-3-2 採集地點與性質 --------------------------------------------- 57 第四章 結果與討論 ------------------------------------------------------ 59 4-1 氣相層析質譜儀對多溴聯苯醚之分析 -------------------------- 59 4-1-1 三至十溴聯苯醚同系物標準品之測定 ------------------ 59 4-1-2 檢量線 --------------------------------------------------------- 60 4-2 加壓溶液萃取技術之最佳化萃取條件 --------------------------- 65 4-2-1 萃取溶液組成 ------------------------------------------------- 65 4-2-2 萃取溫度 ------------------------------------------------------ 68 4-2-3 萃取壓力 ------------------------------------------------------ 69 4-2-4 靜態萃取時間 ------------------------------------------------ 72 4-2-5 動態萃取時間 ------------------------------------------------ 73 4-2-6 前處理方法探討 --------------------------------------------- 76 4-2-6.1 加壓溶液萃取 ---------------------------------------- 76 4-2-6.2 酸洗 ---------------------------------------------------- 77 4-2-7 不同底泥樣品的萃取效果比較 --------------------------- 79 4-2-8 加壓溶液萃取法與傳統索氏萃取法的比較 ------------ 81 4-3 氣相層析質譜儀對環境中多溴聯苯醚同系物濃度之分析 -- 84 4-3-1 環境底泥中多溴聯苯醚之測定 --------------------------- 84 4-3-2 生物檢體中多溴聯苯醚之測定----------------------------- 91 4-4 液相層析質譜儀對多溴聯苯醚之分析 -------------------------- 93 4-4-1 毛細管電壓對分析物感度之影響 ------------------------ 93 4-4-2 汽化溫度對分析物感度之影響 --------------------------- 94 4-4-3 摻雜劑對分析物游離效果的影響 ------------------------ 95 4-4-4 十溴聯苯醚標準品之測定 --------------------------------- 97 4-4-5 檢量線 --------------------------------------------------------- 99 4-5 液相層析質譜儀輔助檢測環境中十溴聯苯醚濃度之分析 - 100 第五章 結論 -------------------------------------------------------------- 105 參考文獻 ------------------------------------------------------------------ 107 表目錄 表1-1. 歷年火災死傷人數及財物損失 ------------------------------- 2 表1-2. 多溴聯苯醚同系物、擬似標準品及內標準品之結構式與 縮寫 ---------------------------------------------------------------- 7 表2-1. 各類耐燃劑之耐燃效果 ----------------------------------------- 13 表2-2. 工業用多溴聯苯醚基本組成 ----------------------------------- 15 表2-3. 1999年多溴聯苯醚全球需求量 ------------------------------- 16 表2-4. 多溴聯苯醚基本性質--------------------------------------------- 17 表2-5. 國外針對多溴聯苯醚同系物之相關研究--------------------- 23 表2-6. 國外針對加壓溶液萃取法檢測多溴聯苯醚同系物之相關 研究 ---------------------------------------------------------------- 25 表2-7. 常用APPI燈源與摻雜劑之估計游離能 -------------------- 39 表3-1. 氣相層析質譜儀參數設定 ------------------------------------- 50 表3-2. SIM mode下不同時間選擇之質荷比 ----------------------- 51 表3-3. 液相層析質譜儀參數設定 ------------------------------------- 52 表3-4. 底泥樣品基本性質 ---------------------------------------------- 58 表4-1. 多溴聯苯醚之偵側極限與檢量線線性關係與相對標準偏 差 ------------------------------------------------------------------- 61 表4-2. 不同萃取溶液組成之回收率與相對標準偏差値------------ 67 表4-3. 不同萃取溫度之回收率與相對標準偏差値 ----------------- 71 表4-4. 不同萃取壓力之回收率與相對標準偏差値 ----------------- 71 表4-5. 不同靜態萃取時間之回收率與相對標準偏差 -------------- 75 表4-6. 不同動態萃取時間之回收率與相對標準偏差値 ----------- 75 表4-7. 不同底泥樣品之添加回收率與相對標準偏差値 ----------- 80 表4-8. 加壓溶液萃取與傳統索氏萃取方法比較 -------------------- 81 表4-9. 加壓溶液萃取與傳統索氏萃取之回收率與相對標準偏差 値---------------------------------------------------------------------- 83 表4-10. 多溴聯苯醚在不同地區底泥中的濃度 ------------------------ 87 表4-11. 多溴聯苯醚在不同底泥基質中的回收率 --------------------- 88 表4-12. 多溴聯苯醚於單口蚓檢體中的濃度 --------------------------- 92 表4-13. 多溴聯苯醚於單口蚓檢體中的回收率 ------------------------ 92 表4-14. 十溴聯苯醚之偵測極限與檢量線線性關係、再現性 ------- 99 表4-15. 以氣相與液相層析質譜儀檢測十溴聯苯醚濃度之比較 --- 100 圖目錄 圖1-1. 歷年火災發生次數 ---------------------------------------------- 2 圖1-2. 四種主要溴化耐燃劑結構圖 ----------------------------------- 2 圖2-1. 添加型耐燃劑分類 ----------------------------------------------- 12 圖2-2. 1997年至2001年台灣地區八溴與十溴聯苯醚進口情形- 16 圖2-3. 多溴聯苯醚與甲狀腺T4激素結構圖 ------------------------ 19 圖2-4. 十溴聯苯醚形成溴化戴奧辛與溴化呋喃之可能機制------ 21 圖2-5. 加壓溶液萃取儀裝置 -------------------------------------------- 27 圖2-6. 四極矩質量分析器 ----------------------------------------------- 33 圖2-7. APPI游離源構造 ------------------------------------------------- 37 圖2-8. 液相層析質譜技術之適用性 ----------------------------------- 40 圖4-1. 分析物標準品之質譜圖 ----------------------------------------- 62 圖4-2. 萃取溶液組成比較 ----------------------------------------------- 66 圖4-3. 萃取溫度比較 ----------------------------------------------------- 70 圖4-4. 萃取壓力比較 ----------------------------------------------------- 70 圖 4-5. 靜態萃取時間比較 ----------------------------------------------- 74 圖4-6. 動態萃取時間比較 ----------------------------------------------- 74 圖4-7. 添加多溴聯苯醚標準品於高嶺土中之加壓溶液萃取層析 圖--------------------------------------------------------------------- 76 圖4-8. 台西地區底泥多溴聯苯醚背景濃度檢測之層析圖 --------- 78 圖4-9. 不同底泥樣品之添加回收率 ------------------------------------ 79 圖4-10. 加壓溶液萃取與傳統索氏萃取檢測固態樣品之層析圖 --- 82 圖4-11. 分析台灣地區底泥之層析圖 ------------------------------------ 89 圖4-12. 分析單口蚓檢體之層析圖 --------------------------------------- 91 圖4-13. 十溴聯苯醚標準品之一次質譜圖 ------------------------------ 94 圖4-14. 毛細管電壓對[M-Br+O]-感度之影響 -------------------------- 94 圖4-15. 汽化溫度對[M-Br+O]-感度之影響 ----------------------------- 95 圖4-16. 摻雜劑種類對分析物游離效果的影響 ------------------------ 96 圖4-17. 摻雜劑比例對分析物游離效果的影響 ------------------------ 97 圖4-18. 十溴聯苯醚之二次質譜圖 --------------------------------------- 98 圖4-19. 十溴聯苯醚之二次質譜選擇離子層析圖 --------------------- 98 圖4-20. LC/MS/MS輔助檢測十溴聯苯醚之層析圖 ------------------- 101 圖4-21. LC/MS/MS輔助檢測十溴聯苯醚之質譜圖 ------------------ 103

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