陳家揚臺灣大學:環境衛生研究所蔡進偉Tsai, Jin-WeiJin-WeiTsai2010-05-072018-06-302010-05-072018-06-302008U0001-2011200812485900http://ntur.lib.ntu.edu.tw//handle/246246/181425近年來飲水中雌激素化合物的存在能否在水處理過程中有效被移除逐漸引起重視。本研究利用固相萃取搭配極致液相層析/串聯式質譜儀調查2007年七月至2008年五月臺灣七家淨水廠七種雌激素化合物於各淨水處理單元之移除效率。分析物包含雌素酮、天然動情激素、雌素醇、乙炔動情激素、雙酚A、辛基酚和壬基酚。 本研究發現原水中雌激素類固醇、雙酚A、辛基酚和壬基酚的幾何平均濃度分別為0.08–0.36 ng/L、0.67 ng/L、2.61 ng/L和87 ng/L，經淨水處理後，其清水中的幾何平均濃度分別為0.05–0.33 ng/L、0.23 ng/L、1.31 ng/L、69 ng/L。而原水中雌激素類固醇、雙酚A、辛基酚和壬基酚的檢出率分別為0.0％–18.8％、33.3％、33.3％和81.3％，經淨水處理後，其清水中的檢出率分別為0.0％–12.5％、0％、8.3％、56.3％，顯示水中低濃度的雌激素類固醇、雙酚A和辛基酚大多可被水處理流程移除至低於偵測極限，而水處理流程似可降低壬基酚含量。 本研究也發現春季原水、沉澱處理後、快濾處理後和清水中壬基酚的平均濃度分別為307 ng/L、294 ng/L、208 ng/L和189 ng/L，顯著大於秋季各淨水流程壬基酚的平均濃度分別為208 ng/L、106 ng/L、52 ng/L和58 ng/L和冬季各淨水流程壬基酚的平均濃度分別為189 ng/L、59 ng/L、62 ng/L和39 ng/L（p<0.05)。此外，春、夏、秋和冬季經所有淨水流程處理後壬基酚之移除率分別為31％、20％、45％和61％。 若生體可利用率為50％和100％時，本研究估計19–64歲年齡層男性個體血清內總天然動情激素之平均當量濃度分別為2.31–2.32 ng/L和4.61–5.76 ng/L，皆為內生性天然動情激素10–50 ng/L的0.05–0.6倍；且19–64歲女性個體血清內總天然動情激素之平均當量濃度分別為2.86–2.89 ng/L和4.62–5.71 ng/L，皆為內生性天然動情激素20–350 ng/L的0.008–0.3倍，顯示國人飲水中受到這些物質導致生殖危害的健康風險極低。There is a concern on the removal of ferminizing chemicals during the drinking water treatment processes. This study investigated the removal of seven estrogenic chemicals during the drinking-water-treatment (DWT) processes from seven plants in Taiwan between July 2007 and May 2008 using solid phase extraction (SPE) and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The analytes were estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2), bisphenol-A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP). We found that geometric mean concentrations of steroid estrogen (E1, E2, EE2 and E3), BPA, OP and NP in raw water were 0.08–0.36 ng/L, 0.67 ng/L, 2.61 ng/L and 87 ng/L, respectively, which were higher than those in finish water, which were 0.05–0.33 ng/L, 0.23 ng/L, 1.31 ng/L and 69 ng/L, respectively. Besides, the detection rate of steroid estrogen, BPA, OP and NP in raw water were 0.0％–18.8％, 33.3％, 33.3％ and 81.3％, respectively, which were higher than those in finished water, which were 0.0％–12.5％, 0％, 8.3％ and 56.3％, respectively. The observations revealed that drinking-water treatment processes could eliminate steroid estrogen, BPA and OP in low concentrations effectively, and decrease the levels of NP in raw water.ean concentrations of NP at each water treatment processes (raw water, sedimentation, rapid filtration and finished water) in spring were 307 ng/L, 294 ng/L, 208 ng/L, and 189 ng/L respectively, which were significantly higher than those in autumn 208 ng/L, 106 ng/L, 52 ng/L, and 58 ng/L, respectively and those in winter 189 ng/L, 59 ng/L, 62 ng/L, and 39 ng/L, respectively (p &lt; 0.05). In addition, the elimination rate of NP after whole treatment processes in spring, summer, autumn and winter were 31％, 20％, 45％ and 61％, respectively.ccording the absorption of these chemicals were 50％ and 100％ respectively, the estimated mean levels of estrogen equivalents (EQ) for 19–64 years old males were 2.31–2.32 ng/L and 4.61–5.76 ng/L, respectively, which were 1.5–21.6 fold lower than normal circulating plasma levels of E2, which were 10–50 ng/L; Moreover, the estimated mean plasma levels of EQ for 19–64 years old females were 2.86–2.89 ng/L and 4.62–5.71 ng/L, respectively, which were 3.0–122.4 fold lower than normal circulating plasma levels of E2, which were 20–350 ng/L, revealing the risk of consumption with drinking water were low.致謝 i文摘要 iibstract iii錄 v目錄 viii目錄 ix一章 前言 1二章 文獻回顧 3.1 雌激素化合物簡介 3.2 雌激素化合物的物化特性和相對活性 4.3 雌激素化合物的環境流佈 5.4 各國對環境荷爾蒙之管制與水質濃度規範 6.5 臺灣飲用水水源與飲用水處理程序 7.5.1 消毒 8.5.2 混凝/沉澱 9.5.3 過濾 9.5.4 活性碳 9.6 樣本前處理 10.7 儀器分析 10三章 研究方法與材料 13.1 試劑與儀器 13.1.1 試劑與材料 13.1.2 儀器設備 14.2 採樣點的選定、採樣步驟及樣品保存 15.3 樣品前處理步驟 15.4 儀器分析條件 16.4.1 極致液相層析儀之條件設定 16.4.2 串聯式質譜儀之條件設定 17.5 品保/品管與檢量線配製 17.5.1. 品保/品管 17.5.2. 檢量線配置製 18.6 統計分析 18.7 生殖風險評估 19四章 結果與討論 21.1 實驗之品保品管 21.1.1 檢量線 21.1.2 回收率與再現性 21.1.3 偵測極限及定量極限 21.1.4 精密度 21.2 各淨水廠水處理流程中環境荷爾蒙濃度範圍、平均濃度、幾何平均濃度和檢出率 22.2.1 各淨水處理流程中環境荷爾蒙的濃度範圍及檢出率 22.2.2 各淨水處理流程中環境荷爾蒙的平均濃度和幾何平均濃度 22.2.3 各淨水處理流程中雌激素類固醇的濃度範圍、平均濃度、幾何平均濃度和檢出率 23.2.4 各淨水處理流程中雙酚A和辛基酚的濃度範圍、平均濃度、幾何平均濃度和檢出率 24.2.5 各淨水處理流程中壬基酚的濃度範圍、平均濃度、幾何平均濃度和檢出率 24.3 水處理流程中壬基酚之含量分布 25.3.1 各淨水廠原水中壬基酚濃度分布 25.3.2 各淨水廠沉澱處理後壬基酚濃度分布 26.3.3 各淨水廠快濾處理後壬基酚濃度分布 27.3.4 各淨水廠清水中壬基酚濃度分布 27.4 各淨水處理流程中壬基酚濃度之季節分布 29.5 雨量、氣溫與原水中壬基酚濃度之關係 30.6 淨水處理後壬基酚移除率之季節分布 31.7 北部、中部和南部淨水廠各淨水流程壬基酚之平均濃度分布 32.8 水質參數與清水中壬基酚年平均濃度 33.9 生殖健康風險評估 33五章 結論與建議 36.1 結論 36.2 建議 37考文獻 38表 51圖 61錄 75錄 一、A淨水廠環境荷爾蒙檢測結果 76錄 二、B淨水廠環境荷爾蒙檢測結果 77錄 三、C淨水廠環境荷爾蒙檢測結果 78錄 四、D淨水廠環境荷爾蒙檢測結果 79錄 五、E淨水廠環境荷爾蒙檢測結果 80錄 六、F淨水廠環境荷爾蒙檢測結果 81錄 七、G淨水廠環境荷爾蒙檢測結果 82application/pdf862237 bytesapplication/pdfen-US雌激素化合物飲水處理過程固相萃取極致液相層析/串聯式質譜儀天然動情激素總天然動情激素當量濃度estrogenic chemicalsdrinking water treatmentsolid–phase extractionultra-performance liquid chromatography-tandem mass spectrometry17β-estradiolestrogen equivalents (EQ)thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/181425/1/ntu-97-R95844004-1.pdf