臺灣博碩士論文加值系統

水體品質向來為整體環境中相當重要之一環，水體品質亦影響人民生活及健康甚鉅。除了常見之水質監測外，近年來許多研究已開始將焦點聚集在環境中新興污染物。目前對於新興污染物是否經由污水處理廠處理不完全而進入水域環境之相關議題被廣為探討，但其排入溪流水體對水域生物的危害則尚未被證實。因此，選定高雄市人口最高亦有事業廢水及生活污水排放之鳳山溪流域進行調查研究。本研究分別於假日及非假日之早上8時、中午14時及晚上20時三個時段採集鳳山溪流域12個樣站，並進行烷基酚類（4n-NP、t-NP、OP、BPA、NP1EO及NP2EO）、驅蟲劑（DEET）、防曬劑類（Benzophenone、4-MBC及BP-3）、抗菌劑類（TCC、PCMX及TCS）、雌激素類（E1、E2、E3、EE2及DES）、防腐劑類（MP、EP、PP及BP）化合物水體濃度分析，藉以探討該流域是否存在平假日之人口活動及污染排放模式差異，此外，針對檢出率最高之化合物進行急慢毒性探討，最後再以新興污染物分析與生物毒性相關性進行生態風險評估之討論。
本研究結果顯示，鳳山溪水質RPI水體狀況為中度污染至嚴重污染，烷基酚類、驅蟲劑類、防曬劑類、抗菌劑類、雌激素類及防腐劑類PCPs (Personal Care Products) 濃度調查結果顯示平、假日差異最大之主要為烷基酚類化合物，假日為平日的1.47倍， NP之差異更是高達2.89倍，推測主要原因為假日中家庭清洗行為增加，導致清潔劑分解後產物濃度上升，此外可以發現抗菌劑類濃度在假日中有明顯的下降趨勢(由33%下降至8%)，經分析後發現主要為平日採樣中P4樣站 778.9 ng/L及P10樣站 644.6 ng/L數據偏高所導致，推測2樣站應有污染來源匯入。
此外，本研究結果顯示BPA平均檢出率高達95.8%，檢測出之濃度介於N.D. ~ 178.8 ng/L，顯示此化合物於環境中廣泛存在，因此，該化合物可能對水生生物造成致死性和亞致死性毒性效應值得更加注意與重視，而高濃度之水體污染是否可能藉由吸附於底泥，進而對底棲生物造成影響，未來可進一步進行調查，已得知較完整之生態風險。

Water quality has always been one of the most important aspects in the process of watershed management due to its potential for affecting people's lives and health directly or indirectly. Studies have begun to focus on emerging environmental contaminants (ECs) in recent years. At present, the issue concerning whether ECs enter watersheds through direct discharge or incomplete treatment by sewage treatment plants is widely discussed, but harmful effects to biota have not been confirmed. The current research investigated ECs such as alkylphenolics (4n -NP, t-NP, OP, BPA, NP1EO, and NP2EO), an insect repellent (DEET), sunscreens (benzophenone, 4-MBC, and BP-3), antibacterial agents (TCC, PCMX, and TCS), estrogens (E1, E2, E3, EE2, and DES) and preservatives (MP, EP, PP, and BP) at 12 sampling sites in the Fengshan River Basin, which has received large amounts of industrial and household wastewaters. Samples were collected from three time-slots, including morning (08:00), noon (14:00), and evening (20:00), and from holiday and non-holiday periods. In addition to chemical analysis, acute and chronic toxicity data are used in collaboration to discuss the ecological risks associated with the compounds that exist in the highest concentrations.
The results show that the water quality of the Fengshan River qualifies under the River Pollution Index (Recchia et al.) as moderately to seriously polluted. The concentrations of alkylphenolic compounds, which are common ingredient in detergents, exhibited marked differences, with holiday samples being 1.47 times higher than non-holiday samples. A difference was also observed in NP, which was 2.89 times higher during holidays than non-holidays. We speculate that increased household cleaning behavior during holidays led to the higher levels of alkylphenolic compounds and their decomposition byproducts being detected. In addition, it was found that the concentrations of antibacterial agents decreased significantly (8-33%) during the holiday period. Triclosan in samples collected from sites P4 and P10 were dramatically decreased from 778.9 ng/L and 644.6 ng/L in weekday sampling. It is speculated that some polluters along these two stations would be the major sources of antibacterial agents.
The results of this study show that the average detection rate of BPA is as high as 95.8% and its concentrations detected by a combination of chemical analysis and toxicological data range from ND to 178.8 ng/L, indicating that BPA is widely present in this watershed. We conclude that BPA has no acute lethality effect; however, its chronic presence deserves more attention. Moreover, considering its high detection rate and physico-chemical properties, the amount of this compound in these sediments can affect benthic organisms. Further investigation should be conducted in order to more completely understand its ecological risks.

摘要 I
Abstract III
謝誌 V
縮寫表 VI
目錄 VII
圖目錄 IX
表目錄 XI
第1章 前言 1
1.1 研究緣起 1
1.2 研究目的 3
第2章 文獻回顧 4
2.1藥物及個人護理產品(PPCPs) 4
2.2目標化合物背景資料 7
2.2.1烷基酚類化合物 13
2.2.2驅蟲劑 15
2.2.3防曬劑類化合物 16
2.2.4抗菌劑類化合物 17
2.2.5雌激素化合物 17
2.2.6防腐劑類化合物 18
2.3 研究地區背景 19
2.3.1 氣候資料 19
2.3.2 水質資料 21
2.3.3 污染現況 21
第3章 材料與方法 23
3.1 實驗材料 23
3.1.1 實驗藥品 23
3.1.2 實驗設備及器材 24
3.2 樣品採集 25
3.2.1 採樣點環境 25
3.2.2 採集頻率 26
3.2.3 水質分析 26
3.3 化學分析 28
3.3.1 樣品前處理製備 28
3.3.2 參數設定 29
3.3.3 品保品管 31
第4章 結果與討論 32
4.1 鳳山溪水質資料 32
4.1.1 pH值 33
4.1.2 水溫 34
4.1.3溶氧 35
4.1.4導電度 36
4.1.5懸浮固體 37
4.1.6 總氮 38
4.1.7生化需氧量(Biochemical Oxygen Demand, BOD5) 42
4.1.8 化學需氧量(Chemical Oxygen Demand, COD) 43
4.1.9 河川污染指標 44
4.2新興污染物分析 46
4.2.1 驅蟲劑 46
4.2.2 防曬劑類 47
4.2.3 抗菌劑類 49
4.2.4 防腐劑類 50
4.2.5 雌激素類 52
4.2.6 烷基酚類 54
4.3 風險評估 57
第5章 結論與建議 60
第6章 參考文獻 73
作者簡介 79

Abdelraheem, W. H. M., He, X., Duan, X., & Dionysiou, D. D. (2015). Degradation and mineralization of organic UV absorber compound 2-phenylbenzimidazole-5-sulfonic acid (PBSA) using UV-254 nm/H2O2. Journal of Hazardous Materials, 282, 233-240.
Ackermann, G. E., Brombacher, E., & Fent, K. (2002). Development of a fish reporter gene system for the assessment of estrogenic compounds and sewage treatment plant effluents. Environmental Toxicology and Chemistry, 21(9), 1864-1875.
Adeel, M., Song, X., Wang, Y., Francis, D., & Yang, Y. (2017). Environmental impact of estrogens on human, animal and plant life: A critical review. Environment International, 99, 107-119.
Ahel, M., Giger, W., & Schaffner, C. (1994). Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment—II. Occurrence and transformation in rivers. Water Research, 28(5), 1143-1152.
Alturki, A. A., Tadkaew, N., McDonald, J. A., Khan, S. J., Price, W. E., and Nghiem, L. D. (2010). Combining MBR and NF/RO membrane filtration for the removal of trace organics in indirect potable water reuse applications. Journal of Membrane Science, 365(1-2), 206-215. doi:10.1016/j.memsci.2010.09.008
Andersen, F. A. (2008). Final amended report on the safety assessment of methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, and benzylparaben as used in cosmetic products. International Journal of Toxicology, 27, 1-82.
Anekwe Jennifer, E., Abou-Elwafa Abdallah, M., and Harrad, S. (2017). Pharmaceuticals and personal care products (PPCPs) in the freshwater aquatic environment. Emerging Contaminants, 3(1), 1-16. doi:10.1016/j.emcon.2016.12.004
Aronson, D., Weeks, J., Meylan, B., Guiney, P. D., & Howard, P. H. (2012). Environmental release, environmental concentrations, and ecological risk of N, N‐Diethyl‐m‐toluamide (DEET). Integrated Environmental Assessment and Management, 8(1), 135-166.
Asimakopoulos, A. G., Thomaidis, N. S., & Koupparis, M. A. (2012). Recent trends in biomonitoring of bisphenol A, 4-t-octylphenol, and 4-nonylphenol. Toxicology Letters, 210(2), 141-154.
Barreiros, L., Queiroz, J. F., Magalhães, L. M., Silva, A. M. T., & Segundo, M. A. (2016). Analysis of 17-β-estradiol and 17-α-ethinylestradiol in biological and environmental matrices — A review. Microchemical Journal, 126, 243-262.
Berryman, D., Houde, F., DeBlois, C., & O'Shea, M. (2004). Nonylphenolic compounds in drinking and surface waters downstream of treated textile and pulp and paper effluents: a survey and preliminary assessment of their potential effects on public health and aquatic life. Chemosphere, 56(3), 247-255.
Birkett, J. W., & Lester, J. N. (2002). Endocrine disrupters in wastewater and sludge treatment processes: IWA Publishing.
Błędzka, D., Gromadzińska, J., & Wąsowicz, W. (2014). Parabens. From environmental studies to human health. Environment International, 67, 27-42.
Burridge, E. (2003). Bisphenol A: product profile. Eur Chem News, 17, 14-20.
Cavalheiro, J., Monperrus, M., Amouroux, D., Preud’Homme, H., Prieto, A., & Zuloaga, O. (2014). In-port derivatization coupled to different extraction techniques for the determination of alkylphenols in environmental water samples. Journal of Chromatography A, 1340, 1-7.
Chen-Hussey, V., Behrens, R., & Logan, J. G. (2014). Assessment of methods used to determine the safety of the topical insect repellent N, N-diethyl-m-toluamide (DEET). Parasites & Vectors, 7(1), 173.
Chisvert, A., Pascual-Martı́, M. C., & Salvador, A. (2001). Determination of the UV filters worldwide authorised in sunscreens by high-performance liquid chromatography: Use of cyclodextrins as mobile phase modifier. Journal of Chromatography A, 921(2), 207-215.
Combalbert, S., & Hernandez-Raquet, G. (2010). Occurrence, fate, and biodegradation of estrogens in sewage and manure. Applied Microbiology and Biotechnology, 86(6), 1671-1692.
Cui, C., Ji, S., & Ren, H. (2006). Determination of steroid estrogens in wastewater treatment plant of a controceptives producing factory. Environmental Monitoring and Assessment, 121(1), 407-417.
Darbre, P., Aljarrah, A., Miller, W., Coldham, N., Sauer, M., & Pope, G. (2004). Concentrations of parabens in human breast tumours. Journal of Applied Toxicology, 24(1), 5-13.
Deblonde, T., Cossu-Leguille, C., and Hartemann, P. (2011). Emerging pollutants in wastewater: a review of the literature. Int J Hyg Environ Health, 214(6), 442-448. doi:10.1016/j.ijheh.2011.08.002
De Laurentiis, E., Minella, M., Sarakha, M., Marrese, A., Minero, C., Mailhot, G., . . . Vione, D. (2013). Photochemical processes involving the UV absorber benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulphonic acid) in aqueous solution: Reaction pathways and implications for surface waters. Water Research, 47(15), 5943-5953.
Di Paolo, C., Kirchner, K., Balk, F. G., Muschket, M., Brack, W., Hollert, H., and Seiler, T. B. (2016). Downscaling procedures reduce chemical use in androgen receptor reporter gene assay. Sci Total Environ, 571, 826-833. doi:10.1016/j.scitotenv.2016.07.059
Di Paolo, C., Ottermanns, R., Keiter, S., Ait-Aissa, S., Bluhm, K., Brack, W., Breitholtz, M., Buchinger, S., Carere, M., Chalon, C., Cousin, X., Dulio, V., Escher, B. I., Hamers, T., Hilscherova, K., Jarque, S., Jonas, A., Maillot-Marechal, E., Marneffe, Y., Nguyen, M. T., Pandard, P., Schifferli, A., Schulze, T., Seidensticker, S., Seiler, T. B., Tang, J., van der Oost, R., Vermeirssen, E., Zounkova, R., Zwart, N., and Hollert, H. (2016). Bioassay battery interlaboratory investigation of emerging contaminants in spiked water extracts - Towards the implementation of bioanalytical monitoring tools in water quality assessment and monitoring. Water Res, 104, 473-484. doi:10.1016/j.watres.2016.08.018
European Commission., 1994, “Commission regulation (ec) no 1488/94 of 28 june 1994 laying down the principles for the assessment of risks to man and the environment of existing substances in accordance with council regulation (eec) no 793/93 (text with eea relevance)”, in Official Journal of the European Community L vol. 161pp. 3-11.
Gao, D., Li, Z., Guan, J., & Liang, H. (2017). Seasonal variations in the concentration and removal of nonylphenol ethoxylates from the wastewater of a sewage treatment plant. Journal of Environmental Sciences, 54, 217-223.
Giokas, D. L., Salvador, A., & Chisvert, A. (2007). UV filters: From sunscreens to human body and the environment. TrAC Trends in Analytical Chemistry, 26(5), 360-374.
Golden, R., Gandy, J., & Vollmer, G. (2005). A review of the endocrine activity of parabens and implications for potential risks to human health. Critical Reviews in Toxicology, 35(5), 435-458.
Gould, J. C., Leonard, L. S., Maness, S. C., Wagner, B. L., Conner, K., Zacharewski, T., . . . Gaido, K. W. (1998). Bisphenol A interacts with the estrogen receptor α in a distinct manner from estradiol. Molecular and Cellular Endocrinology, 142(1–2), 203-214.
Han, J., Won, E.-J., Hwang, U.-K., Kim, I.-C., Yim, J. H., & Lee, J.-S. (2016). Triclosan (TCS) and Triclocarban (TCC) cause lifespan reduction and reproductive impairment through oxidative stress-mediated expression of the defensome in the monogonont rotifer (Brachionus koreanus). Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 185–186, 131-137.
Hsieh, C.-Y., Yang, L., Kuo, W.-C., & Zen, Y.-P. (2013). Efficiencies of freshwater and estuarine constructed wetlands for phenolic endocrine disruptor removal in Taiwan. Science of The Total Environment, 463, 182-191.
Isidori, M., Cangiano, M., Palermo, F. A., and Parrella, A. (2010). E-screen and vitellogenin assay for the detection of the estrogenic activity of alkylphenols and trace elements. Comp Biochem Physiol C Toxicol Pharmacol, 152(1), 51-56. doi:10.1016/j.cbpc.2010.02.011
Kitchen, L. W., Lawrence, K. L., & Coleman, R. E. (2009). The role of the United States military in the development of vector control products, including insect repellents, insecticides, and bed nets. Journal of Vector Ecology, 34(1), 50-61.
Manová, E., von Goetz, N., Hauri, U., Bogdal, C., & Hungerbühler, K. (2013). Organic UV filters in personal care products in Switzerland: A survey of occurrence and concentrations. International Journal of Hygiene and Environmental Health, 216(4), 508-514.
Mathieu-Denoncourt, J., Wallace, S. J., de Solla, S. R., and Langlois, V. S. (2016). Influence of Lipophilicity on the Toxicity of Bisphenol A and Phthalates to Aquatic Organisms. Bull Environ Contam Toxicol, 97(1), 4-10. doi:10.1007/s00128-016-1812-9
Matsuda, Brent M.; Surgeoner, Gordon A.; Heal, James D.; Tucker, Arthur O.; Maciarello, Michael J. (1996). Essential oil analysis and field evaluation of the citrosa plant "Pelargonium citrosum" as a repellent against populations of Aedes mosquitoes. Journal of the American Mosquito Control Association, 12 (1), 69–74.
Nakada, N., Tanishima, T., Shinohara, H., Kiri, K., and Takada, H. (2006). Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment. Water Res, 40(17), 3297-3303. doi:10.1016/j.watres.2006.06.039
Peng, X., Wang, Z., Yang, C., Chen, F., & Mai, B. (2006). Simultaneous determination of endocrine-disrupting phenols and steroid estrogens in sediment by gas chromatography–mass spectrometry. Journal of Chromatography A, 1116(1), 51-56.
Pouillot, A., Polla, B., & Polla, A. (2006). Conservateurs en cosmétologie: mise au point sur les Parabènes. Journal de médecine esthétique et de chirurgie dermatologique, 33(131), 187-190.
Ramos, S., Homem, V., Alves, A., & Santos, L. (2015). Advances in analytical methods and occurrence of organic UV-filters in the environment — A review. Science of The Total Environment, 526, 278-311.
Recchia, A., Vivacqua, A., Gabriele, S., Carpino, A., Fasanella, G., Rago, V., . . . Maggiolini, M. (2004). Xenoestrogens and the induction of proliferative effects in breast cancer cells via direct activation of oestrogen receptor α. Food Additives and Contaminants, 21(2), 134-144.
Renner, R. (1997). European bans on surfactant trigger transatlantic debate. Environmental Science & Technology, 31(7), 316A-320A.
Ruggeri, B., Ubaldi, M., Lourdusamy, A., Soverchia, L., Ciccocioppo, R., Hardiman, G., Baker, M. E., Palermo, F., and Polzonetti-Magni, A. M. (2008). Variation of the genetic expression pattern after exposure to estradiol-17beta and 4-nonylphenol in male zebrafish (Danio rerio). Gen Comp Endocrinol, 158(1), 138-144. doi:10.1016/j.ygcen.2008.05.012
Sciences, N. I. o. E. H. (1994). Seventh annual report on carcinogens: Summary. Research Triangle Park, North Carolina: US Department of Health and Human Services.
Servos, M. R. (1999). Review of the aquatic toxicity, estrogenic responses and bioaccumulation of alkylphenols and alkylphenol polyethoxylates. Water Quality Research Journal of Canada, 34(1), 123-177.
Sole M, Lopez de Alda MJ, Castillo M, Porte C, Ladegaard-Pedersen K, Barcelo D. (2000). Estrogenicity determination in sewage treatment plants and surface waters from the Catalonian area (NE Spain). Environ Sci Technol,34,5076 –5083.
Soni, M., Carabin, I., & Burdock, G. (2005). Safety assessment of esters of p-hydroxybenzoic acid (parabens). Food and Chemical Toxicology, 43(7), 985-1015.
Taylor, M., & Harrison, P. (1999). Ecological effects of endocrine disruption: current evidence and research priorities. Chemosphere, 39(8), 1237-1248.
Terzic, S., Senta, I., Ahel, M., Gros, M., Petrovic, M., Barcelo, D., Muller, J., Knepper, T., Marti, I., Ventura, F., Jovancic, P., and Jabucar, D. (2008). Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. Sci Total Environ, 399(1-3), 66-77. doi:10.1016/j.scitotenv.2008.03.003
Trenholm, R. A., Vanderford, B. J., Drewes, J. E., and Snyder, S. A. (2008). Determination of household chemicals using gas chromatography and liquid chromatography with tandem mass spectrometry. J Chromatogr A, 1190(1-2), 253-262. doi:10.1016/j.chroma.2008.02.032
Trenholm, R. A., Vanderford, B. J., Holady, J. C., Rexing, D. J., and Snyder, S. A. (2006). Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry. Chemosphere, 65(11), 1990-1998. doi:10.1016/j.chemosphere.2006.07.004
Welshons, W. V., Thayer, K. A., Judy, B. M., Taylor, J. A., Curran, E. M., & Vom Saal, F. S. (2003). Large effects from small exposures. I. Mechanisms for endocrine-disrupting chemicals with estrogenic activity. Environmental Health Perspectives, 111(8), 994.
Wright-Walters, M., Volz, C., Talbott, E., and Davis, D. (2011). An updated weight of evidence approach to the aquatic hazard assessment of Bisphenol A and the derivation a new predicted no effect concentration (Pnec) using a non-parametric methodology. Sci Total Environ, 409(4), 676-685. doi:10.1016/j.scitotenv.2010.07.092
Yamazaki, E., Yamashita, N., Taniyasu, S., Lam, J., Lam, P. K., Moon, H. B., Jeong, Y., Kannan, P., Achyuthan, H., Munuswamy, N., and Kannan, K. (2015). Bisphenol A and other bisphenol analogues including BPS and BPF in surface water samples from Japan, China, Korea and India. Ecotoxicol Environ Saf, 122, 565-572. doi:10.1016/j.ecoenv.2015.09.029
Ying, G.-G., Kookana, R. S., & Ru, Y.-J. (2002). Occurrence and fate of hormone steroids in the environment. Environment International, 28(6), 545-551.
Yu, C.-P., Deeb, R. A., & Chu, K.-H. (2013). Microbial degradation of steroidal estrogens. Chemosphere, 91(9), 1225-1235.
吳孟純. (2012). 污水處理廠去除個人防護用品及放流水質對承受水體之評估探討. 屏東科技大學, Retrieved from http://dx.doi.org/10.6346/NPUST.2012.00270
林正芳等人. (2008). 新興汙染物 (抗生素與止痛藥) 於特定汙染源環境之流佈.
林怡秀. (2017). 承受畜牧廢水溪流水體之離體雌激素活性與雌激素濃度評估. 屏東科技大學,
高雄市政府環境保護局. (2013). 高雄市河川水質統計與優劣分析探討.
高雄市政府環境保護局. (2016). 104年度高雄市鳳山溪流域管理計畫.
張上淳, 陳美文, 林美智, and 胡幼圃. (2003). 台灣人用抗生素與動物用抗生素使用量之調查研究. 感染控制雜誌, 第13卷第6期, 334-345.
郭旭芩. (2014). 溪流中雄性尼羅口孵魚之卵黃前質基因表現與內分泌干擾物質之流佈探討. 屏東科技大學, Retrieved from http://dx.doi.org/10.6346/NPUST.2014.00039
楊子君. (2008). 利用生物彗星檢定法評估人工濕地壬基苯酚毒性變化之可行性研究. 屏東科技大學,
劉鎮彰. (2010). 探討雄性大鼠暴露於壬基苯酚與辛基苯酚之不同組織殘量分佈. 屏東科技大學, Retrieved from http://dx.doi.org/10.6346/NPUST.2010.00166