臺灣博碩士論文加值系統

四氯異苯腈(chlorothalonil)為非系統性殺真菌劑，主要防治對象為小葉菜類葉斑病，亦能延伸應用於不同的作物，但其對魚及水生無脊椎生物具有高毒性，可能造成水體環境汙染；對眼睛及呼吸系統有腐蝕性。目前國內公告測定之方法為使用氣相層析串聯質譜儀（GC-MS/MS）測定作物中的四氯異苯腈殘留，但常有分析物訊號不穩定之情形；國際上歐盟農藥殘留參考實驗室(EURL)也有液相層析串聯質譜儀(LC-APCI-MS/MS)分析四氯異苯腈的相關方法，但靈敏度仍不甚理想。本研究參考檢測蔬果中農藥殘留的QuEChERS方法，以液相層析串聯譜儀(LC-MS/MS)結合本實驗室之放電套頭(discharge adaptor interface, DA interface）介面，開發檢測蔬果中四氯異苯腈殘留之分析方法，修飾後的QuEChERs方法與以往方法相比較為簡單，能減少前處理時間及分析成本，使用等梯度沖提分析樣品，方法定量極限(LOQ)為5 ng/g，檢量線範圍為5-200 ng/g，並且有良好的線性(r2 > 0.99)，精密度(CV%，3濃度，6重複)皆小於15 %，而準確度(%Error，3濃度，6重複)皆在± 15 %範圍內。以此方法分析了8件田間蔬果，其中番茄檢出濃度為9.5 ng/g，菠菜有一件檢出濃度為2588.9 ng/g，其他皆未檢出。
在國內使用抗凝血型殺鼠劑防治鼠害，其主要作用機制為干擾維生素K和其環氧化物的循環代謝。然而在使用抗凝血殺鼠劑防治鼠類也有可能對於非目標野生動物的造成毒害，抗凝血殺鼠劑容易累積於脊椎動物肝臟中，因此本研究參考D. Vudathala 之前處理方法進行修飾，以0.5 g肝臟加入8 mL ACN萃取，離心後取上清液加入4 mL淨化液，震盪離心，取ACN層吹乾回溶後，同樣使用液相層析串聯質譜儀結合自行開發之放電套頭介面同步分析鳥類肝臟中13 項抗凝血殺鼠劑。本方法之定量極限（LOQ）為0.1-5 ng/g，檢量線範圍為 0.1-100 ng/g，在鳥肝中得到良好的線性 (r2> 0.99)。方法精密度(CV%)小於15%，準確度(%Error)位於±15%內。本研究所檢測之動物肝臟樣品由屏科大所提供，共計11件樣品。其中有5件樣品有檢出，檢出率為45.5 %，檢出藥劑為bromadiolone (撲滅鼠) 濃度為1.1-121.8 ng/g、flocoumafen(伏滅鼠) )濃度為5.1-36.2 ng/g、brodifacoum (可滅鼠)濃度為4.3-53.5 ng/g 、difethialone (達滅鼠)濃度為1.5 ng/g。

Chlorothalonil(2,4,5,6-tetrachloroisobenzonitrile) is a broad spectrum, non-systemic protectant pesticide mainly used as a fungicide to control fungal foliar diseases of vegetable and various crops. However, it is highly toxic to fish and aquatic inverte-brates and may cause water pol-lution. In Taiwan the current official method for de-termination is to use gas chromatography-tandem mass spectrometry (GC-MS/MS) to determine the residues of chlorothalonil in crops, but the signal stability is often un-satisfied. The European Union Reference Laboratories for Residues of Pesticides (EURL) also reported an analytical method for chlorothalonil by using the liquid chromatography tandem mass spectrometery (LC-APC-MS/MS) with APCI interface. The LOQ of 10 ng/g was achieved, but a dedicate APCI probe is required.
In this study, the liquid chromatography tandem spectrometer (LC-MS/MS) combined with the discharge adaptor interface (DA interface) of our laboratory are applied to determine the residure of chlorothalonil in vegetables.A modified QuEChERs method was also developed to improve signal sensitivity. The measured limit of quantification (LOQ) was 5 ng/g. The calibration curve was ranged at 5-200 ng/g, and it has good linearity (r2> 0.99), precision (CV%, 3 levels 6 repeats) was less than 15%, and the measured accuracy (%Error, 3 level, 6 deprecates) was within ± 15%. Eight samples of field fruits and vegetables were analyzed with the developed method, among the samples, 9.5 ng/g of chlorothalonil was detected in one tomato sample, 2588.9 ng/g of chlorothalonil was detected in one spinach sample, and no residue was detected for other 6 samples.
Anticoagulant rodenticides are used for rodent control. However, the use of anticoag-ulant rodenticides may also cause toxicity to non-target organism. Besides, are easily accumulateds in liver of vertebrates.
To add the evaluation of the effect of rodenticides on non-target organisms,in this study. The LC-MS/MS with DA interface was also used to determine 13 anticoagu-lant rodenticides in the liver samples from wildlife birds .The liver samples (0.5 g) were homogenized extracted with 8 mL of acetonitrile (ACN) with adding of sodium chloride. The measured limit of quantification (LOQ) of this method is 0.1-5 ng/g. The calibration curve was measurement range prepared at 0.1-100 ng/g in chicken liver, and good linearity was obtained (r-square >0.99). The method validation performed by the spiked chicken liver samples (3 spiked levels, 6 replicates), the measured accu-racy (%Error) was less than ±15% and the measured precision (CV%) was less than 15%. The developed method was applied to determine the residues of 13 anticoagu-lant rodenticides in 11 liver samples of wild birds. The residues of rodencides were detected in 5 liver samples 45.5% detection rate. The detected agents were bromadio-lone ranged at 1.1-121.8 ng/g,flocoumafen ranged at 5.1-36.2 ng/g, brodifacoum ranged at 4.3-53.5 ng/g difethialone ranged at 1.5 ng/g.

中文摘要......i
英文摘要......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
1.1.1四氯異苯腈(Chlorothalonil)......1
1.1.2抗凝血殺鼠劑(Anticoagulant rodenticides )......1
1.2 危害及降解......2
1.2.1四氯異苯腈之危害及降解......2
1.2.2抗凝血殺鼠劑之危害......3
1.3歷年分析文獻......5
1.3.1四氯異苯腈之歷年分析文獻......5
1.3.2殺鼠劑之歷年分析文獻......5
1.4 液相層析串聯質譜儀(LC-MS/MS)......6
1.4.1 大氣壓化學游離法(APCI)......7
1.4.2 電灑游離法(ESI)......7
1.4.3 放電套頭介面(Discharge Adaptor, DA interface)......8
1.5 研究動機......9
第二章 材料與方法......10
2.1藥品及實驗材料......10
2.1.1 標準品......10
2.1.2 試劑與材料......10
2.2 儀器設備及器材......11
2.3 標準品與內部標準品儲備溶液配製......11
2.4 樣品前處理方法......13
2.4.1蔬果樣品前處理方法......13
2.4.2 鳥肝樣品前處理方法......14
2.5 液相層析串聯質譜方法......14
2.5.1 四氯異苯腈液相層析條件......14
2.5.2 殺鼠劑液相層析條件......15
2.5.3 質譜參數設定......15
2.6 四氯異苯腈方法性能測試......16
2.6.1線性與偵測極限測試......16
2.6.2 準確度與精密度測試......16
2.6.3基質效應測試......16
2.7 實際蔬果樣品分析......16
2.8 殺鼠劑方法性能測試......16
2.8.1線性與偵測極限測試......16
2.8.2 準確度與精密度測試......17
2.8.3基質效應測試......17
2.9 實際鳥肝樣品分析......17
第三章 四氯異苯腈分析結果與討論......18
3.1 蔬果樣品中四氯異苯腈分析......18
3.1.1四氯異苯腈及4-OH-2,5,6-三氯異苯腈之質譜分析......18
3.1.2 LC-MS/MS分析農藥標準品......19
3.2 樣品萃取方法測試......20
3.2.1 萃取方法及條件測試......20
3.2.2 共萃物比較......21
3.3 方法性能測試......22
3.3.1 方法線性範圍及方法偵測極限......22
3.3.2 精密度及準確度......22
3.4 蔬果樣品分析......22
第四章 抗凝血殺鼠劑分析結果與討論......24
4.1 鳥肝樣品中殺鼠劑分析......24
4.1.1 殺鼠劑標準品之質譜分析......24
4.1.2 LC-MS/MS分析農藥標準品......25
4.2 放電套頭介面與電灑法之比較......26
4.3 樣品萃取方法測試......26
4.4 方法性能測試......27
4.4.1 方法線性範圍及方法偵測極限......27
4.4.2 精密度及準確度......27
4.4.3 基質效應測試......27
4.5 野鳥肝臟樣品分析......28
4.6 相關文獻分析結果......29
第五章 結論......31
參考文獻......87
英文論文......96

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