本研究利用液相層析串聯式質譜儀分析水體中烷基苯酚聚乙氧基醇含量，並比較液液萃取法與固相萃取法萃取環境水體中烷基苯酚聚乙氧基醇化合物之優劣。在回收率上，以固相萃取法表現優於液液萃取法，壬基苯酚聚乙氧基醇與辛基苯酚聚乙氧基醇回收率分別為62.3-110.7 % 與64.9-112.0 %；在回收率穩定性上，也是固相萃取法表現較優，壬基苯酚聚乙氧基醇與辛基苯酚聚乙氧基醇標準偏差分別為1.22-7.97 %，因此本研究在樣品分析上選擇以固相萃取法做為萃取方法，並使用C18作為固萃匣的吸附劑。最低偵測極限分別為17.60-174.9 ng/L與7.40-53.56 ng/L。
本研究針對高雄市愛河流域，在2011年6月採集八個測站進行環境水體中烷基苯酚聚乙氧基醇含量分析。其總烷基苯酚聚乙氧基醇濃度最高值出現在位於愛河上游的明誠橋(52.00 μg/L)。在所有採樣點中，以明誠橋之辛基苯酚四乙氧基醇在所有化合物中濃度最高(11.84 μg/L)。另外，辛基苯酚聚乙氧基醇濃度(128.04 μg/L)比壬基苯酚聚乙氧基醇(20.11 μg/L)還高。

A LC-MS/MS method for the analysis of alkylphenol polyethoxylates in environmental waters was developed in this study. Preatment procedures including liquid-liquid extraction and solid phase extraction were compared, it’s concluded that solid phase extraction is the more suitable way due to higher recovery and better stability for the analytical results. The recovery of nonylphenol polyethoxylate and octylphenol polyethoxylate were 62.3-110.7 % and 64.9-112.0 %, limit of detection were 17.60-174.9 ng/L and 7.40-53.56 ng/L.
Enviromental water samples were collected from eight sampling sites along Love River in Kaohsiung City to investigate the contents of alkylphenol polyethoxylates. The highest concentration of total alkylphenol polyethoxylates was observed at Ming-Cheng Bridge which located at the upstream of Love River. For all of the analyzed compounds, the concentration of octylphenol tetraethoxylate (40.46 μg/L) was the highest in all of the sampling sites. It’s also noticed the concentration of octylphenol polyethoxylate (20.11 μg/L) was higher than that of nonylphenol polyehtoxylate (128.04 μg/L).

學位論文審定書 I
摘要 II
Abstract III
目錄 IV
表次 VI
圖次 VII

壹、前言 1
一、研究緣起 1
二、研究目的 2
貳、文獻回顧 3
一、環境荷爾蒙 3
(一)環境荷爾蒙概述 3
(二)環境荷爾蒙來源、作用機制與影響 4
二、烷基苯酚聚乙氧基醇化合物 7
(一)烷基苯酚聚乙氧基醇化合物概述 7
(二)烷基苯酚聚乙氧基醇化合物降解機制 9
(三)國內外烷基苯酚聚乙氧基醇含量與相關管制政策 10
三、水體萃取方法 12
(一)液液萃取法 12
(二)固相萃取法 12
(三)固相萃取法吸附劑種類 13
四、儀器偵測方法 15
(一)液相層析串聯式質譜儀 16
(二)電灑式離子化器 16
參、實驗材料與分析方法 18
一、實驗藥品與材料 18
二、儀器設備 19
三、分析方法 20
(一)標準品製備 20
(二)液相層析串聯式質譜儀參數條件 21
(三)環境水體之採集與前處理 25
(四)水樣中分析物液相萃取法 26
(五)水樣中分析物固相萃取法 28
肆、結果與討論 30
一、水樣中液相萃取法方法最佳化 30
(一)萃取溶劑之選擇 30
(二)水與有機相比例對回收率之影響 32
(三)萃取次數對回收率之影響 34
二、水樣中固相萃取法方法最佳化 36
(一)水樣進樣體積對回收率之影響 36
(二)流析溶劑對回收率之影響 36
(三)液液萃取法與固相萃取法比較 41
三、液相層析移動相成份之探討 44
(一)以手配標準品 (100 ng/L) 測試 44
(二)環境水體對層析圖譜之影響 47
四、品保與品管 52
(一)校正曲線 52
(二)儀器偵測極限、最低偵測極限與最低定量極限 56
(三)水樣萃取回收率 60
五、愛河河水中烷基苯酚含量分析 64
(一)水文資料 64
(二)愛河中烷基苯酚聚乙氧基醇含量分析 65
(三)今昔愛河中烷基苯酚聚乙氧基醇含量比較 72
(四)國外文獻中水樣之烷基苯酚聚乙氧基醇含量比較 73
伍、結論 75

參考文獻 76

(1) 林礽麒：可怕的環境荷爾蒙，安立出版社，民國92年。
(2) 卓俊良：利用液相層析串聯質譜儀對水體及沉積物中烷基苯酚化合物分析方法之研究，碩士論文，國立中山大學海洋生物科技暨資源研究所，民國98年。
(3) 陳仁坤：利用液相層析串聯質譜儀探討高雄市主要河川及港區水域烷基苯酚化合物之分布，碩士論文國立中山大學海洋生物科技暨資源研究所，民國95年。
(4) 陳永仁：環境荷爾蒙管制，財團法人孫運璿學術基金會，民國90年。
(5) 毒性化學物質風險簡介，毒性化學物質安全管理策略規劃及減量評估計畫，行政院環境保護署，民國96年。
(6) Colborn, T., Saal, F. S., Soto, A. M. (1993) Developmental Effects of Endocrine-Disrupting Chemicals in Wildlife and Humans, Environ. Health Perspec., 101(5), 378-384.
(7) Ferguson, P. L., Iden, C. R., Brownawell, B. J. (2000) Analysis of Alkylphenol Ethoxylate Metabolites in the Aquatic Environment Using Liquid Chromatography-Electrospray Mass Spectrometry, Anal. Chem., 2000, 72, 4322-4330.
(8) Ferrara, F., Ademollo, N., Delise, M., Fabietti, F., Funari, E. (2008) Alkylphenols and their ethoxylates in seafood from the tyrrhenian sea, Chemosphere, 72, 1279–1285.
(9) Fountoulakis, M., Drillia, P., Pakou, C., Kampioti, A., Stamatelatou, K., Lyberatos, G. (2005) Analysis of nonylphenol and nonylphenol ethoxylates in sewage sludge by high performance liquid chromatography following microwave-assisted extraction, J. Chromatogr. A, 1089, 45–51.
(10) Guenther, K., Heinke, V., Thiele, B., Kleist, E., Prast, H., Raecker, T. (2002) Endocrine disrupting nonylphenols are ubiquitous in food, Environ. Sci. Technol., 36, 1676-1680.
(11) Isobe, T., Nishiyama, H., Nakashima, A., Takada, H. (2001) Distribution and behavior of nonylphenol, octylphenol, and nonylphenol monoethoxylate in tokyo metropolitan area: their association with aquatic particles and sedimentary distributions, Environ. Sci. Technol., 35, 1041-1049.
(12) Jimenez-Diaz, I., Ballesteros, O., Zafra-Gomez, A., Crovetto, G., Vilchez, J. L., Navalon, A., Verge, C., Ferrer, J. A. (2010) New sample treatment for the determination of alkylphenols and alkylphenol ethoxylates in agricultural soils, Chemosphere, 80 (3), 248-255.
(13) Koh, Y. K. K., Chiu, T. Y., Boobis, A. R., Cartmell, E., Pollard, S. J. T., Scrimshaw, M. D., Lester, J. N. (2008) A sensitive and robust method for the determination of alkylphenol polyethoxylates and their carboxylic acids and their transformation in a trickling filter wastewater treatment plant, Chemosphere, 73, 551–556.
(14) Li, D., Kim, M., Shim, W. J., Yim, U. H., Oh, J. R., Kwon, Y. J.(2004) Seasonal flux of nonylphenol in Han River, Korea, Chemosphere, 56, 1-6
(15) McLachlan, J. A. (2001) Environmental Signaling: What Embryos and Evolution Teach Us About Endocrine Disrupting Chemicals, Endocrine Reviews, 22 (3), 319-341.
(16) Petrovic, M., Sole, M., Lo Pez De Alda, M. J., Barcelo, D. (2002) Endocrine disruptors in sewage treatment plants, receiving river waters, and sediments: integration of chemical analysis and biological effects on feral carp, Environ. Toxicol. Chem., 21, 2146-2156.
(17) Shao, B., Hu, J. Y., Yang, M. (2002) Determination of nonylphenol ethoxylates in the aquatic environment by normal phase liquid chromatography–electrospray mass spectrometry, J. Chromatogr. A, 950, 167–174.

(18) Vega-Morales, T., Sosa-Ferrera, Z., Santana-Rodriguez, J. J. (2010) Determination of alkylphenol polyethoxylates, bisphenol-A, 17α-ethynylestradiol and 17β-estradiol and its metabolites in sewage samples by SPE and LC/MS/MS, J. Haz. Mater., 183, 701-711.
(19) Vega-Morales, T., Torres-Padron, M. E., Sosa-Ferrera, Z., Santana-Rodriguez, J. J. (2009) Determination of alkylphenol ethoxylates and their degradation products in liquid and solid samples, Trends Anal. Chem., 28 (10), 1186-1200.
(20) Voutsa, D., Hartmann, P., Schaffner, C., Giger, W. (2006) Benzotriazoles, Alkylphenols and Bisphenol A in Municipal Wastewaters and in the Glatt River, Switzerland, Environ Sci Pollut Res, 13 (5), 333 – 341.
(21) Werme, C. (2009) Endocrine-Disrupting Chemicals: Surveillance Using Bay Fish, Regional Monitoring Program Update.
(22) Yu, Y., Zhai, H., Hou, S., Sun, H. (2009) Nonylphenol ethoxylates and their metabolites in sewage treatment plants and rivers of Tianjin, China, Chemosphere, 77, 1-7.