臺灣博碩士論文加值系統

有機氯劑農藥為持久性有機污染物-為揮發性低、不易分解之疏水性物質，其半衰期甚長，在環境中不易分解。聯合國環境計畫(United Nations Environment Programme, UNEP)中，定義出十二種持久性有機污染物(persistent organic po1lutants, POPs)，包括阿特靈(aldrin)、可氯丹(ch1ordane)、滴滴涕（dichloro-diphenyl- trichloroethan, DDT）、地特靈(dieldrin)、安特靈(endrin)、飛佈達(heptachlor)、蟲必死(hexachlorocyclohexane, BHC)、滅蟻樂(mirex)、毒殺芬(toxaphene)等九種有機氯劑農藥，以及戴奧辛(dioxin)、呋喃(furans)、多氯聯苯(polychlorinated biphenyls, PCBs)等三種有機氯工業產品及副產品，並於2001年起全面禁用或嚴格限用此十二種持久性有機污染物。由於上述十二種持久性有機氯劑在環境中會經由食物鏈的生物濃縮效應，在生物體產生累積，其中生物體中脂肪為累積有機氯劑的主要組織。所以脂肪含量高的蛋類、畜肉及食用油脂為人類累積有機氯農藥的暴露途徑之一，因此為了解該類食品中有機氯劑之含量情形，乃利用萃取、淨化和 GC 分析定量，再以 GC/MS/MS 鑑定，來探討市售蛋類、畜肉及食用油脂之十四種有機氯劑的殘留量。結果顯示，上述定性、定量檢測法均具靈敏性，經分析200件檢體，顯示受檢全部蛋類皆未檢出；畜肉中有9件檢出4,4’-DDE，含量範圍0.018~0.516 ppm (脂肪基準)；食用油脂有10件檢體檢出殘留有機氯劑，包括4,4’-DDE (0.002~ 0.063 ppm)、 4,4’-DDT (0.012~0.14 ppm)、lindane (0.002~0.006 ppm)、��-BHC (0.008 ppm)及 ��-BHC (0.003 ppm)。我國國家標準中，對於此十二種持久性有機污染物，在蛋類和肉類均設有標準，上述檢測值均在標準值以下。另外我國食用油脂尚未設定標準，若依美國國家標準值規定，上述國內食用油脂之有機氯劑殘留量，亦均在其標準值以下。顯示國內這些食品，尚有部分含有有機氯劑，但其殘留量均在人體安全攝食範圍之內。

Organochlorine pesticides are low volatile, hydrophobic compounds which are not easily decomposed in environment. United Nations Environment Programme (UNEP) defined 12 persistent organic pollutants（POPs）, including organochlorine pesticides (aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, BHC, mirex, and toxaphene) and other three kinds of organochlorine industry products and byproducts (PCBs, dioxin and furans) which had been either banned or subjected to severe use restrictions since 2001. Organochlorine pesticides, due to their environmental persistence, could accumulate in biological lipid tissue through food chain. The food, including eggs, meats and edible fat and oils, having high lipid levels become one of the routes for human exposing to organochlorine pesticides. To investigate 14 kinds of organochlorine pesticide residues in food, the methods were developed to analyze the residues in eggs, meats and edible fat and oils. Briefly, sample lipid was extracted by solvent, cleaned up by cartridge, analyzed by GC-ECD and conformed by GC-MS-MS. The studies showed that the sensitivities of the methods in both qualification and quantification were good. Two hundred samples were analyzed by the developed methods and the results showed all tested eggs were not detected; 9 meat samples contained 4,4’-DDE (0.018 – 0.516 µg/g lipid); 10 edible oil samples contained 4,4’-DDE (0.002 – 0.063 µg/g lipid), 4,4’-DDT(0.012 – 0.14 µg/g lipid), lindane (0.002 – 0.006 µg/g lipid), α-BHC (0.008 µg/g lipid) and β-BHC (0.003 µg/g lipid). The organochlorine pesticide residues in egg samples and meat samples were in compliance with the regulation of Department of Health. The organochlorine pesticide residues were also in compliance with the criteria of US national standards. Although the organochlorine pesticide residues were found in food in this study, the residue levels have no health impact on human.

中文摘要………………………………………………………………1
英文摘要………………………………………………………………3
論文縮體字總表………………………………………………………5
壹、前言………………………………………………………………6
貳、文獻回顧…………………………………………………………8
參、材料與方法………………………………………………………14
一、試驗材料……………………………………………………14
二、儀器設備與裝置……………………………………………14
三、試藥…………………………………………………………15
四、標準溶液之配置……………………………………………16
五、檢液製備……………………………………………………16
六、檢量線之製作………………………………………………19
七、鑑別試驗及含量測定………………………………………19
八、氣相層析儀之分析條件……………………………………19
九、氣相層析離子阱質譜儀之分析條件………………………20
十、回收試驗……………………………………………………20
十一、最低檢出限量試驗………………………………………21
肆、結果與討論………………………………………………………22
一、檢液製備……………………………………………………22
二、有機氯劑之檢測……………………………………………23
三、檢量線………………………………………………………24
四、最低檢出限量………………………………………………24
五、添加回收試驗………………………………………………25
六、台灣地區蛋類、畜肉及食用油脂中有機氯劑殘留量檢驗結
果……………………………………………………………26
七、與國內外檢驗結果之比較…………………………………28
八、風險評估 ………………………………………………… 29
伍、結論…………………………………………………………… 31
陸、參考文獻……………………………………………………… 32
柒、表次
表1、台灣地區對持久性有機污染物中有機氯劑之管制情形……38
表2、有機氯劑之毒性、毒性分類及每日容許攝取量……………39
表3、2002年有機氯劑於台灣地區魚貝類殘留檢驗結果……… 40
表4、鳥巢中有機氯劑於鳥蛋污染之情形……………………… 41
表5、智利不同種鳥類所生蛋中殘留有機氯劑之情形………… 42
表6、加拿大歷年來不同鳥類其蛋中殘留有機氯劑之調查結果比
較…………………………………………………………… 43
表7、不同豬肉組織中DDT及其衍生物之濃度………………… 44
表8、不同豬肉組織中BHC及其異構物之濃度………………… 45
表9、印度地區油脂中殘留之有機氯劑………………………… 46
表10、禽畜水產品中殘留持久性污染物標準比較……………… 47
表11、有機氯劑之氣相層析質譜/質譜條件…………………… 49
表12、添加於雞蛋中有機氯劑以GC/ECD檢測之檢量線之線性回歸方程
式和相關係數及最低檢出限量………………… 50
表13、添加於豬肉脂肪中有機氯劑以GC/ECD檢測之檢量線之線性回歸
方程式和相關係數及最低檢出限量…………… 51
表14、添加於大豆沙拉油中有機氯劑以GC/ECD檢測之檢量線之線性回
歸方程式和相關係數及最低檢出限量………… 52
表15、有機氯劑之氣相層析質譜/質譜之檢出限量…………… 53
表16、雞蛋和豬肉脂肪中添加有機氯劑之回收率……………… 54
表17、大豆沙拉油中添加有機氯劑之回收率…………………… 55
表18、台灣地區畜肉中十四有機氯劑殘留調查結果…………… 56
表19、台灣地區食用油脂中十四有機氯劑殘留調查結果……… 57
表20、台灣地區蛋類及畜肉中有機氯劑殘留量調查…………… 58
表21、台灣地區食用油脂中有機氯劑殘留量調查……………… 59
表22、不同採樣區域之畜肉中有機氯劑殘留量調查…………… 60
表23、不同生產國別之畜肉中有機氯劑殘留量………………… 61
表24、不同生產國別之食用油脂中有機氯劑殘留量…………… 62
表25、2002-2005年台灣地區各類食品檢出有機氯劑情形…… 63
表26、台灣和美國蛋類中殘留有機氯劑調查結果比較………… 64
表27、1998年及2004年台灣地區畜肉中殘留有機氯劑調查結果比
較………………………………………………………65
表28、不同國家畜肉中殘留有機氯劑調查結果比較…………… 66
表29、不同國家食用油脂中殘留有機氯劑調查結果比較……… 67
表30、畜肉中殘留有機氯劑之風險評估………………………… 68
表31、食用油脂中殘留有機氯劑之風險評估…………………… 69
捌、圖次
圖1、持久性污染物有機氯劑之化學結構式………………………70
圖2、加拿大歷年來不同鳥類其蛋中有機氯劑之調查結果比
較…………………………………………………………… 71
圖3、蛋類中有機氯劑農藥萃取之實驗流程…………………… 72
圖4、畜肉之前處理……………………………………………… 73
圖5、食用油脂之前處理………………………………………… 74
圖6、肉類及食用油脂中有機氯劑農藥之淨化步驟…………… 75
圖7、萃取溶媒量對大豆沙拉油中有機氯劑之回收增加率…… 76
圖8、十四種有機氯劑對照用標準品之氣相層析圖譜………… 77
圖9、雞蛋添加十四種有機氯劑之氣相層析圖譜……………… 78
圖10、豬肉脂肪添加十四種有機氯劑之氣相層析圖譜………… 79
圖11、大豆沙拉油添加十四種有機氯劑之氣相層析圖譜……… 80
圖12、��-BHC等十四種有機氯劑之子離子重組層析圖………… 81
圖13、BHC、HCB、heptachlor及heptachlor epoxide之質譜
圖…………………………………………………………… 82
圖14、Aldrin、chlordane、dieldrin及endrin之質譜圖…… 83
圖15、DDE、DDT及mirex之質譜圖……………………………… 84
圖16、雞蛋中添加十四種有機氯劑之最低檢出限量…………… 85
圖17、豬肉脂肪中添加十四種有機氯劑之最低檢出限量……… 86
圖18、食用油脂中添加十四種有機氯劑之最低檢出限量……… 87
附錄
附錄1、93年檢體採樣紀錄及檢驗結果……………………………88
附錄2、94年檢體採樣紀錄及檢驗結果……………………………92

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