臺灣博碩士論文加值系統

就衛生及環境毒理學之觀點，水產品重金屬污染問題一直是受到關注之課題，本研究之目的為開發有機汞及有機錫分析方法，並建立魚類中有機汞物種和重金屬暨貝類中有機錫和重金屬之含量資料庫。
首先，為建立以微波輔助消化、乙基化或丙基化及氣相層析質譜法分析魚類中之有機汞含量。將檢體0.5 g置微波消化瓶中，加四甲基氫氧化銨溶液 5 mL，以聚焦式微波消化器加熱消化後，以醋酸中和，加入醋酸銅溶液及醋酸緩衝溶液，再加入四乙基硼酸鈉/氫氧化鉀溶液（乙基化）或四丙基硼酸鈉/氫氧化鉀溶液（丙基化）衍生化，以正庚烷震盪萃取，靜置分層後取上層液以氣相層析質譜儀分析。實驗結果顯示，最佳微波消化條件為15–30 W加熱 3.5分鐘、45 W加熱2.5 分鐘或60–75 W加熱1 分鐘。最佳衍生化條件為於pH 5下添加1%四乙基硼酸鈉/氫氧化鉀或 pH 4下添加1%四丙基硼酸鈉/氫氧化鉀溶液反應10分鐘。氣相層析質譜儀分析條件為注射口溫度230℃，管柱溫度 60℃維持5分鐘，再以20℃/分鐘昇溫，以CP-Sil 8 CB Low Bleed/MS 毛細管管柱分離，其可於10分鐘內完成分析。本方法之魚肉樣品有機汞偵測極限為 0.040 mg/g。
添加 0.5、1.0及 2.0 mg/g甲基汞及無機汞於魚肉中，以建立汞物種乙基化方法分析，其回收率為92.3–96.4%及93.6–95.5%。分析三種參考物質之甲基汞含量，BCR CRM 464 tuna fish為5.31 ± 0.32 mg/g（標示值為5.50 ± 0.17 mg/g），NRCC DOMR-2 dog fish muscle為4.40 ± 0.34 mg/g （標示值為4.47 ± 0.32 mg/g）及 DOLT-2 dogfish liver為0.663 ± 0.061 mg/g（標示值為0.693 ± 0.053 mg/g）。
另添加0.5、1.0及2.0 mg/g甲基汞、乙基汞及無機汞於魚肉中，以建立汞物種丙基化方法分析，其回收率為91.2–94.7%、93.8–97.8%及 94.3–97.4%。其次，分析三種參考物質之甲基汞含量，BCR CRM 464 tuna fish為5.34 ± 0.30 mg/g (標示值 5.50 ± 0.17 mg/g)，NRCC DORM-2 dogfish muscle為4.34 ± 0.24 mg/g (4.47 ± 0.32 mg/g)及DOLT-2 dogfish liver為0.652 ± 0.055 mg/g (0.693 ± 0.053 mg/g)。顯示此二種方法皆適用於魚肉中汞物種之分析。
其次，為建立以微波輔助消化、丙基化及氣相層析質譜法分析螺貝類中有機錫含量。乃將檢體 0.5 g置微波消化瓶中，加四甲基氫氧化銨溶液 5 mL，以聚焦式微波消化器加熱消化後，以醋酸中和，加入醋酸緩衝溶液（pH 4），再加入四丙基硼酸鈉/氫氧化鉀溶液衍生化，以異辛烷震盪萃取三次，合併萃取液減壓濃縮後，以氣相層析合併化學游離質譜儀分析。實驗結果顯示，最佳微波消化條件為微波功率 45 W加熱消化 3.0分鐘。最佳衍生化條件為於 pH 4下添加 1%四丙基硼酸鈉/氫氧化鉀溶液反應 10分鐘。氣相層析質譜儀分析條件為注射口溫度 240℃，管柱溫度 60℃維持 5分鐘，再以10℃/分鐘昇溫，以 CP-Sil 8 CB Low Bleed/MS 毛細管管柱分離，其可於 20分鐘內完成分析。本方法之樣品有機錫偵測極限為 0.020 mg/g。添加 0.5、1.0及 2.0 mg/g有機錫於文蛤及牡蠣中，其回收率分別為單丁基錫 69.3–77.3%及67.1–74.4%，二丁基錫 89.3–92.7%及87.2–93.6%，三丁基錫 92.1–97.2%及94.7–98.6%，四丁基錫 92.5–95.2%及95.4–98.2%。其次，分析參考物質 BCR CRM 477 mussel tissue之有機錫含量，單丁基錫為 1.33 ± 0.38 mg/g （標示值 1.50 ± 0.28 mg/g），二丁基錫為 1.62 ± 0.23 mg/g（1.54 ± 0.12 mg/g），三丁基錫為 2.35 ± 0.16 mg/g（2.20 ± 0.19 mg/g）。顯示本方法適用於螺貝類中有機錫物種之分析。
利用上述汞物種分析方法和一般重金屬分析方法分析591件魚類檢體，結果得知汞總平均值為0.881 mg/g (0.01–13.8 mg/g)，甲基汞總平均值為0.639 mg/g (＜0.04–10.9 mg/g)，鋅含量總平均值為7.56 mg/g (1.98–34.3 mg/g)，鎘含量總平均值為0.022 mg/g (0.002–0.176 mg/g)；鉛含量總平均值為0.022 mg/g (0.002–0.249 mg/g)；銅含量總平均值為0.957 mg/g (0.11–8.13 mg/g)；鎳含量總平均值為0.037 mg/g (<0.02–0.380 mg/g)及錫含量總平均值為0.012 mg/g (<0.02–0.095 mg/g)。
另以上述有機錫之分析方法合一般重金屬分析方法分析市售貝類檢體100件，結果得知鉛含量總平均值為0.116 mg/g (<0.004–0.343 mg/g)；鎘含量總平均值為0.114 mg/g (<0.001–0.538 mg/g)；鎳含量總平均值為0.228 mg/g (<0.002–1.091 mg/g)；鉻含量總平均值為0.155 mg/g (0.007–0.625 mg/g)；銅含量總平均值為37.5 mg/g (0.10–348.2 mg/g)；鋅含量總平均值為87.7 mg/g (4.6–580.9 mg/g)。有機錫含量含量總平均值單丁基錫為34.6 ng/g (<20–234.3 ng/g)，二丁基錫為37.0 ng/g (<20–206.0 ng/g) ，三丁基錫為43.5 ng/g (<20–376.0 ng/g)，四丁基錫為12.7 ng/g (<20–89.4 ng/g)。

The pollution problem of seafood with heavy metals is still a concerning issue judging from both hygienic and ecotoxicological points of view. The purpose of this study is to develop the analysis method of organic mercury and tin, and then establish the database of the organic mercury and heavy metals in fish, and organic tin and heavy metals in shellfish.
The analytical procedure for analysis of mercury species in fish was developed. It involved microwave-assisted digestion with alkaline solution (tetramethylammonium hydroxide), neutralization using acetic acid, addition of Cu++ and acetate buffer (pH 5) aqueous-phase derivatization with sodium tetraethylborate or acetate buffer (pH 4) aqueous-phase derivatization of mercury species with sodium tetrapropylborate, and subsequent extraction with n-heptane. The various mercury derivatives were desorbed in the splitless injection port of a gas chromatograph and subsequently analyzed by electron impact mass spectrometry. Optimum conditions allowed sample through out to be controlled by the instrumental analysis time (near 10 min per sample) but not by the sample preparation step. At the power of 15–30, 45, 60–75 W, sample preparation time is only 3.5, 2.5, and 1.5 min, respectively. The proposed method was finally validated by the analysis of three biological certified reference materials, BCR CRM 464 tuna fish, NRC DORM-2 dogfish muscle, and NRC DOLT-2 dogfish liver. The detection limit of the overall procedure was found to be 0.040 mg/g of biological tissue for mercury species. The recoveries of mercury species were 92.3–96.4% and 93.6–95.5% for methyl- and inorganic mercury of ethylation, and 91.2–94.7%, 93.8–97.8%, and 94.3–97.4% for methyl-, ethyl-, and inorganic mercury of propylation, respectively. The detected and certified values of methylmercury of three biological certified reference materials were as follows: 5.31 ± 0.32 mg/g (mean ± S.D.) mg/g and 5.50 ± 0.17 mg/g for BCR CRM 464 tuna fish, 4.40 ± 0.34 mg/g and 4.47 ± 0.32 mg/g for NRCC DORM-2 dogfish muscle, and 0.663 ± 0.061 mg/g , and 0.693 ± 0.053 mg/g for NRCC DOLT-2 dogfish liver for ethylation, and 5.34 ± 0.30 for BCR CRM 464 tuna fish, 4.34 ± 0.24 mg/g for NRCC DORM-2 dogfish muscle and 0.652 ± 0.055 mg/g for NRCC DOLT-2 dogfish liver for propylation, respectively. It indicated that the method was well available to detect the mercury species in fish.
The analytical procedure for butyltin in oyster was developed. It involved microwave-assisted digestion with alkaline solution (tetra methylammonium hydroxide), neutralization using acetic acid, aqueous-phase derivatization with sodium tetrapropylborate, and subsequent extraction with isooctane. The various butyltin derivatives were desorbed in the splitless injection port of a gas chromatograph and subsequently analyzed by chemical ionization mass spectrometry. Optimum conditions allowed sample throughput to be controlled by the instrumental analysis time (near 19 min per sample) but not by the sample preparation step. At the irradiation power of 45 W, sample heating time is only 3.0 min. The proposed method was finally validated by the analysis of biological certified reference materials (BCR CRM 477 mussel tissue). The detection limit of the overall procedure was found to be 0.020 mg/g of biological tissue for butyltin species. The recoveries of butyltin species of clam and oyster were 69.3–77.3% and 67.1–74.4%, 89.3–92.7% and 87.2–93.6%, 92.1–97.2% and 94.7–98.6%, and 92.5–95.2% and 95.4–98.2% for MBT, DBT, TBT, and TeBT, respectively. The detected and certified values of butyltin of BCR CRM 477 mussel tissue were as follows: 1.33 ± 0.38 (mean ± S.D.) mg/g and 1.50 ± 0.28 mg/g for MBT, 1.62 ± 0.23 mg/g and 1.54 ± 0.12 mg/g for DBT, 2.35 ± 0.16 mg/g and 2.20 ± 0.19 mg/g for TBT, respectively. It indicated that the method was well available to detect the butyltin species in oyster.
Adopted AAS, AFS and GC-MS method to analyze 591 fish samples. The results showed that total average content of Hg, MeHg, Zn, Cd, Pb, Cu, Ni, and Sn were 0.881 mg/g (0.01–13.8 mg/g), 0.639 mg/g (＜0.04–10.9 mg/g), 7.56 mg/g (1.98–34.3 mg/g), 0.022 mg/g (0.002–0.176 mg/g), 0.022 mg/g (0.002–0.249 mg/g), 0.957 mg/g (0.11–8.13 mg/g), 0.037 mg/g (<0.02–0.380 mg/g) and 0.012 mg/g (<0.02–0.095 mg/g).
Adopted AAS and GC-MS method to analyze 190 shellfish samples which were purchased from markets. The results showed that total average content of Pb, Cd, Ni, Cr, Cu, Zn, MBT, DBT, TBT and TeBT were 0.116 mg/g (<0.004–0.343 mg/g), 0.114 mg/g (<0.001–0.538 mg/g, 0.228 mg/g (<0.002–1.091 mg/g), 0.155 mg/g (0.007–0.625 mg/g), 37.5 mg/g (0.10–348.2 mg/g), 87.7 mg/g (4.6–580.9 mg/g), 4.6 ng/g (<20–234.3 ng/g), 37.0 ng/g (<20–206.0 ng/g), 43.5 ng/g (<20–376.0 ng/g) and 12.7 ng/g (<20–89.4 ng/g).

中文摘要…………………………………………………………… 1
英文摘要…………………………………………………………… 4
本論文發表狀況…………………………………………………… 7
研究背景及目的…………………………………………………… 9
文獻整理…………………………………………………………… 11
第一章 魚類中有機汞乙基化及氣相層析質譜檢測方法之探討
一﹑前言…………………………………………………………… 25
二﹑材料與方法…………………………………………………… 27
三、結果與討論…………………………………………………… 35
結論……………………………………………………………… 46
圖表………………………………………………………………… 47
第二章 魚類中有機汞丙基化及氣相層析質譜檢測方法之探討
一﹑前言…………………………………………………………… 71
二﹑材料與方法…………………………………………………… 72
三、結果與討論…………………………………………………… 80
結論………………………………………………………………… 91
圖表………………………………………………………………… 92
第三章 台灣漁船捕獲魚類之有機汞及其他重金屬含量
一﹑前言…………………………………………………………… 115
二﹑材料與方法…………………………………………………… 117
三、結果與討論…………………………………………………… 123
結論………………………………………………………………… 141
圖表………………………………………………………………… 142
第四章 貝類中有機錫丙基化及氣相層析質譜檢測方法之探討
一﹑前言…………………………………………………………… 179
二﹑材料與方法…………………………………………………… 181
三、結果與討論…………………………………………………… 189
結論……………………………………………………………… 200
圖表………………………………………………………………… 201

第五章 台灣市售貝類之有機錫及其他重金屬含量
一﹑前言…………………………………………………………… 223
二﹑材料與方法…………………………………………………… 226
三、結果與討論…………………………………………………… 231
結論………………………………………………………………… 245
圖表………………………………………………………………… 246
總結論……………………………………………………………… 273
參考文獻…………………………………………………………… 275
謝辭………………………………………………………………… 287

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