臺灣博碩士論文加值系統

甲基汞可能存在於各種不同的環境介質中，包含水體、土壤與底泥，故準確的定量甲基汞為所有後續研究之基礎。環保署環檢所於九十八年公告了水中甲基汞檢測方法(NIEA W540.50B)，使用公告方法進行水中甲基汞測定，但方法蒸餾後水體樣品之接收液酸鹼度過低(pH < 3)，造成所得甲基汞回收率過低(5–6%)。調整為密閉條件後，可使蒸餾之接收液酸鹼值維持於4–5之間，如此回收率便可大幅提升(88–102%)。土壤前處理程序則分別採用美國Brooks Rand實驗室與美國地質調查所(USGS)之建議方法，使用土壤標準品CRM測試。結果Brooks Rand方法回收率(91%)較USGS方法(57%)高。本研究整合USGS與Brooks Rand方法，可有效節省前處理時間由兩天縮短至六小時。平均回收率為91±8%，範圍為75–102%，方法偵測極限為13.2 pg g-1。實際測定受到汞污染廠址的海水池底泥結果顯示甲基汞範圍介於1.00–6.38 ng g-1。血液使用Liang等人於2000年提出之方法外加些微修改，血液標準品SRM回收率為122%，實際血液甲基汞範圍從4.11–7.14 ng g-1。

Methylmercury may exist in various media, including water, soil, sediment, and biological tissues. Quantification of methylmercury in trace amounts is an important task, which is based on different sample pretreatments that liberate methylmercury from its matrix into Mili-Q water and the methylmercury can be subsequently determined. Taiwan EPA in 2009 proposed standard aqueous methylmercury determination method (NIEA W540. 50B). This study examined the proposed method to quantify methylmercury in water sampled from contaminated sites. Experimental Results showed that the distillate pH was below 3 based on Taiwan EPA method. The low pH was suspected to cause a low recovery of 5–6%. A modified distillation process was performed, namely, distilling the sample in a closed vessel without purging gases. Results showed that the recovery of methylmercury can significantly increase to 88–102%.
To determine methylmercury in soils, methods established by Brooks Rand laboratory and US Geological surveys’ (USGS) were chosen and examined. The analytical results showed that the recovery obtained from Brooks Rand method was greater (91.37%) than that from the USGS method (56.70%). However, it takes two days to get analytical results with Brooks Rand method. We tried to combine the USGS and Brooks Rand method, results showed that it took about six hours to obtain reliable data. The modified combined method was evaluated by analyzing two certified reference materials (SQC-1238、ERM-CC580). The recovery was within 75.8–102% with an average of 91.03±8.47% (MDL = 13.2 pg g-1). The modified method was used to quantify methylmercury in contaminated sediments sampled from a chlor-alkali factory; methylmercury concentration ranged between 1.00 and 6.38 ng g-1. Blood methylmercury was measured followed the method proposed by Liang et al (2000) with minor modifications. The method was preliminary evaluated by analyzing the standard reference material (SRM 955c). Recovery was shown to be 122%. Methylmercury in the tested maternal blood and cord blood ranged between 4.11 and 7.14 ng g-1.

摘要 i
Abstract ii
誌謝 iv
目錄 v
第一章 前言 1
1.1 研究源起 1
1.2 研究目的 3
第二章 文獻回顧 4
2.1 背景 4
2.1.1 全球汞排放量 4
2.1.2 汞的危害 5
2.2汞物種型態和循環 7
2.2.1 汞物種型態 7
2.2.2 甲基汞 7
2.2.3 汞循環 8
2.3 近期甲基汞相關研究 9
2.4 甲基汞分析方法 12
2.4.1 甲基汞分析方法介紹 12
2.5 水體中甲基汞分析前處理方法 13
2.6 土壤中甲基汞分析前處理方法 15
2.6.1 各種前處理方法 15
2.6.2 前處理方法比較 16
2.7 血液甲基汞前處理方法 18
2.8 土壤中汞物種分析 19
2.9 序列萃取分析方法 20
2.10 品質控制 23
第三章 材料與方法 24
3.1 研究架構 24
3.2 研究材料與樣本 26
3.3水體甲基汞前處理方法 27
3.3.1 水體前處理試劑與材料 27
3.3.2 水體甲基汞前處理步驟 29
3.4土壤甲基汞前處理方法 30
3.4.1土壤前處理試劑與材料 30
3.4.2 BrooksRand 前處理步驟 30
3.4.3 USGS前處理步驟 31
3.4.4 三因子實驗設計 31
3.5血液甲基汞前處理方法 33
3.5.1血液前處理試劑與設備 33
3.5.2血液前處理步驟 33
3.6 甲基汞分析 34
3.6.1甲基汞分析設備 34
3.6.2甲基汞分析使用試劑與氣體 35
3.6.3清洗 36
3.6.4甲基汞分析程序與品質控制 36
3.6.5方法偵測極限 37
3.7總汞溶出實驗 38
3.7.1總汞分析設備所需溶劑和氣體 38
3.7.2總汞溶出實驗使用試劑與材料 39
3.7.3樣品和檢量線總汞溶出前處理步驟 40
3.8汞之序列萃取實驗 41
3.8.1汞之序列萃取設備、試劑、材料和氣體 41
3.9 有機質含量測定 43
3.10 統計方法簡述 43
第四章 結果與討論 45
4.1 甲基汞標準品訊號 45
4.2 水體甲基汞前處理程序 46
4.3 土壤甲基汞測定前處理程序 48
4.4 汞污染底泥實際測定 56
4.5 血液甲基汞測定方法 66
第五章 結論 69
5.1 結論 69
5.2 建議 70
參考文獻 71
附件一 SQC-1238 認證文件 77
附件二 ERM-CC580認證文件 79
附件三 SRM 955c 認證文件 81
附件四 土壤、血液實驗記錄表格 87

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