農藥的使用在農業生產的產量及品質上扮演一個很重要的角色，然而，過多的農藥可能殘留於環境中(如:河川、土壤等)，造成環境危害。除草劑為常使用農藥種類之一，其中除草劑-嘉磷塞(glyphosate)和固殺草(glufosinate)為目前世界上最常使用的除草劑，由於其極高之水溶性，造成分析上的困難，因此本研究嘗試建立可用於河水和底泥中嘉磷塞、嘉磷塞代謝物(AMPA)與固殺草之殘留分析方法，此方法使用相對應之穩定同位素作為內標準品，以Fluorenylmethyloxycarbonyl chloride (FMOC-Cl)於硼酸緩衝溶液下進行衍生化，再以固相萃取匣淨化濃縮。其後以液相層析串聯質譜對各FMOC-衍生物進行偵測分析。以10mL水樣進行確效試驗，水樣中各分析標準品之檢量線範圍可達7.8-2000.0 ng/L:R2均大於0.997以上，測試偵測極限(S/N ratio≧3):嘉磷塞為1.4 ng/L、AMPA為1.7 ng/L和固殺草為0.7 ng/L，精密度(CV%，3種濃度，6重複)範圍為2.35-14.71 %，而準確度(%Error，3種濃度，6重複)可達±10.00 %以內。在真實河水樣品中(共分析32樣品)，可測得嘉磷塞(105年27.1-1353.9 ng/L；106年32.4-1111.3 ng/L)、AMPA (105年60.2-1440.5 ng/L；106年67.5-1509.0 ng/L)、固殺草(105年20.0-178.0 ng/L；106年14.8-503.1 ng/L)的殘留。對底泥樣品，則先以鹼性水溶液進行萃取後，加入內標物再經FMOC-Cl衍生化與固相萃取，再以液相層析串聯質譜進行分析各FMOC-衍生物。以2 g底泥經萃取液獲得「空白土壤樣品」進行確效試驗，土壤各分析標準品之檢量線範圍可達0.78-100.0 ng/g，R2均大於0.998以上，測試偵測極限(以S/N ratio≧3估算):嘉磷塞為0.12 ng/g、AMPA為0.08 ng/g及固殺草為0.04 ng/g，測得精密度(CV%，3濃度，6重複)範圍為2.07-7.96%，而準確度(%Error，3濃度，6重複)可達±4.83%以內。在真實土壤樣品中(共32個樣品)，可測得嘉磷塞(105年4.0-189.6 ng/g；106年2.4-34.7 ng/g) 及AMPA(105年3.3-233.6 ng/g；106年1.8-84.7 ng/g) ；固殺草檢出濃度則多為未檢出。

Glyphosate (N-(phosphonomethyl) glycine) and glufosinate (ammonium dl-homoalanin- 4-(methyl) phosphinate) are nonselective, broad spectrum, and highly polar herbicides which are wildly used for weed control in aquatic systems and vegetation control in non-crops areas. In addition, aminomethylphosphonic acid (AMPA) is the major degradation product of glyphosate presented in plants, water and soil samples. To address the concerns to its environmental residue and the possible adverse effects, two analytical methods for determining glyphosate, glufosinate and AMPA in river water and sediment samples were developed, respectively. The methods applied 9-Fluorenylmethyloxycarbonyl chloride (FMOC-Cl) derivertization, solid phase extraction (SPE) and LCMS/MS analysis of the synthesized FMOC-derivatives. The stable isotope internal standards for each analyte were also used. For the water sample analysis, the linear range was obtained from 7.8 to 2000.0 ng/L (r2 >0.997), the estimated detection limits (S/N ratio≧3) were 1.4 ng/L of glyphosate, 1.7 ng/L of AMPA and 0.7 ng/L of glufosinate. The obtained CV% of the spiked water samples (3 levels, 6 replicates ) were ranged at 2.35-14.71%, and the mean %Error of were -10.00~5.49% of glyphosate, -1.54~3.43% of AMPA and 0.17~5.77% of glufosinate. For the sediment analysis, the samples were firstly extracted with 0.6M KOH (aq) and cleaned up with SPE, and then prepared as water sample. The linear range was obtained from 0.78 to 100.00 ng/g (r2 >0.998), the estimated detection limits (S/N ratio≧3) were 0.12 ng/g of glyphosate, 0.08 ng/g of AMPA and 0.04 ng/g of glufosinate. The obtained CV% (3 levels, 6 replicates) of the spiked sediment samples were ranged at 2.07-7.96%, and the %Error were -2.54 to 4.33 % of glyphosate, -4.84 to 3.66 % of AMPA and -3.15 to-0.79 % of glufosinate, respectively.
The developed methods were used to analyze 32 water samples and 32 sediment samples that were collected from agricultural district of southern Taiwan (16 water and 16 sediment samples were received in 2016, and 16 water and 16 sediment samples were received in 2017). For the water samples, residue of glyphosate was found in 15 samples in 2016 (93.4% detected), ranged at 27.1-1353.9 ng/L, and 15 samples in 2017 (93.4% detected), ranged at 32.4-1111.3 ng/L. The residues of AMPA were found in 15 samples in 2016 (93.4% detected), ranged at 60.2-1440.5 ng/L, and 15 samples in 2017 (93.4% detected), ranged at 67.5-1509.0 ng/L. The residues of glufosinate were found in 4 samples in 2016 (25% detected), ranged at 20.0-178.0 ng/L, and 6 samples in 2017 (37.5% detected), ranged at 14.8-503.1 ng/L. For the sediment samples, residues of glyphosate were found in 14 samples in 2016 (87.5% detected), ranged at 4.0-189.6 ng/g, and 13 samples in 2017 (81.3% detected), ranged at 2.4-34.7 ng/g. The residues of AMPA were found in 16 samples in 2016 (100% detected), ranged at 3.3-233.6 ng/g, and 15 samples in 2017 (93.4% detected), ranged at 1.8-84.7 ng/g. The residues of glufosinate in the sediment samples were not detected.

摘要........................................... i
Abstract....................................... iii
誌謝........................................... v
目錄........................................... vi
表目錄......................................... ix
圖目錄.......................................... x
第一章 緒論..................................... 1
1.1 前言....................................... 1
1.2文獻回顧..................................... 2
1.2.1嘉磷塞(Glyphosate, 嘉磷塞)介紹:............ 2
1.2.2固殺草(Glufosinate)介紹:.................. 6
1.2.3嘉磷塞(Glyphosate)與固殺草(Glufosinate)之歷年分析方法............................................. 8
1.3 液相層析串聯式質譜儀(LC-MS/MS).............. 14
1.3.1電灑游離法(ESI)............................ 14
1.4研究動機..................................... 16
第二章 材料與方法............................... 17
2.1 藥品及實驗材料.............................. 17
2.1.1 標準品................................... 17
2.1.2 試劑與材料................................ 17
2.1.3 環境樣品來源.............................. 17
2.2 儀器設備及器材.............................. 18
2.3 標準品與內部標準品儲備溶液配製............... 19
2.4標準品直接分析............................... 21
2.5層析條件測試................................. 21
2.6標準品化學衍生法............................. 21
2.7河川水樣品前處理方法.......................... 22
2.7.1衍生化反應之測試........................... 22
2.7.2固相萃取匣(Solid Phase Extraction, SPE)破出(Breakthough)之測試............................. 22
2.7.3固相萃取匣(SPE)沖提體積之測試............... 23
2.8 液相層析串聯質譜方法......................... 23
2.8.1最終液相層析條件........................... 23
2.8.2質譜參數設定............................... 24
2.9 河川水方法性能測試.......................... 24
2.9.1線性與偵測極限............................. 24
2.9.2準確度與精密度測試.......................... 25
2.9.3不同來源基質效應測試........................ 25
2.10底泥樣品前處理方法........................... 25
2.10.1萃取試劑最佳化之測試....................... 25
2.10.2衍生化反應之測試.......................... 26
2.11 液相層析串聯質譜方法........................ 27
2.11.1最終液相層析條件.......................... 27
2.12 底泥方法性能測試........................... 27
2.12.1線性與偵測極限............................ 27
2.12.2準確度與精密度測試......................... 28
2.12.3不同來源基質效應測試....................... 28
2.13 真實樣品分析............................... 28
2.13.1河川水樣品分析............................ 28
2.13.2底泥樣品分析.............................. 29
第三章 結果與討論............................... 30
3.1標準品之測試................................. 30
3.1.1未衍生化標準品之質譜分析.................... 30
3.1.2未衍生化標準品之LC-MS/MS分析................ 30
3.2標準品之化學衍生法............................ 31
3.2.1衍生化標準品之質譜分析...................... 31
3.2.2衍生化標準品之LC-MS/MS分析.................. 32
3.3 河川水前處理方法之最佳化..................... 33
3.3.1衍生化反應時間之測試........................ 33
3.3.2去除試劑溶劑............................... 33
3.3.3固相萃取匣破出(breakthough)之測試........... 34
3.3.4沖提體積之測試............................. 34
3.4 河川水方法性能測試........................... 34
3.4.1線性範圍與方法偵測極限...................... 34
3.4.2精密度與準確度............................. 35
3.4.3不同來源的基質效應測試...................... 35
3.5底泥前處理方法之最佳化........................ 36
3.5.1萃取試劑最佳化之測試........................ 36
3.5.2衍生化反應時間之測試........................ 36
3.8 底泥分析方法性能測試......................... 37
3.8.1線性範圍與方法偵測極限...................... 37
3.8.2精密度與準確度............................. 37
3.8.3不同來源的基質效應測試...................... 38
3.9真實樣品分析................................ 38
3.9.1河川水樣品分析............................. 38
3.9.2底泥樣品分析............................... 40
第四章 結論..................................... 42
參考文獻........................................ 128
Extended Abstract.............................. 139
簡歷(CV)....................................... 152

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