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研究生: 余致廣
Yu, Chih-Kuang
論文名稱: 污水處理廠中內分泌干擾活性及個人保健用品之濃度變化和二苯甲酮類氯化衍生物之活性探討
Variation of endocrine disrupting activities and levels of personal care products in wastewater treatment plants and endocrine disrupting activities of chlorinated benzophenones
指導教授: 周佩欣
Chou, Pei-Hsin
學位類別: 碩士
Master
系所名稱: 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 145
中文關鍵詞: 污水處理廠個人保健用品報導基因酵母菌試驗法液相層析串聯式質譜儀內分泌干擾活性二苯甲酮對羥基苯甲酸酯抗菌劑消毒劑
外文關鍵詞: Personal care products, Endocrine disrupting chemicals, Liquid chromatography tandem mass spectrometry, Yeast-based reporter gene assays, Chlorinated derivatives, Parabens, Antimicrobials, Disinfectants
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  • 隨著經濟和技術的發展,個人保健用品 (Personal care products, PCPs)被廣泛添加於日常產品中,以增加其功能性。伴隨著民眾大量地使用,PCPs及其代謝物都可能進到民生污水處理廠,當這些污染物質無法有效被去除時,則會透過排放進到自然水體,因此有必要了解其在污水處理流程中之變化。
    本研究採集臺灣四座民生污水處理廠各處理單元之出流水及廢棄污泥,使用報導基因酵母菌試驗法檢測樣本之內分泌干擾活性,並以液相層析串聯式質譜儀檢測常見之PCPs,包括防曬劑、防腐劑、抗菌劑及消毒劑在處理過程中的濃度變化。研究中亦將常見之三種防曬劑,2-羥基-4-甲氧基二苯甲酮、5-氯-2-羥基二苯甲酮及2,2'-二羥基-4-甲氧基二甲酮進行氯化,並進一步分析其衍生物之結構、內分泌干擾活性、與進、出流水中之濃度。
    內分泌干擾活性試驗表明,二苯甲酮類物質大多具有抗雄激素活性、類(抗)雌激素活性、抗鹽皮質激素活性及抗孕激素活性,其氯化衍生物亦具有抗雄激素、抗雌激素、抗鹽皮質激素及抗孕激素活性。此外,在所有污水廠的放流水中仍然可測得抗鹽皮質激素活性,表示抗鹽皮質激素物質會進到環境水體中。
    液相層析串聯式質譜儀分析結果顯示,各污水廠放流水中總二苯甲酮的濃度範圍為94 至 420 ng/L,其中以二苯甲酮及2,2'-二羥基-4,4'-二甲氧基二苯甲酮之濃度最高。此外,於第一季放流水中皆有測得2-羥基-4-甲氧基二苯甲酮之氯化衍生物,濃度範圍為0.85至3.63 ng/L。於各污水廠之進流水中,對羥基苯甲酸甲酯及對羥基苯甲酸丙酯之檢出頻率及濃度都較高,不過經污水處理後都可以有效之去除,去除效率介於87至98%間。污泥中測得較高濃度之三氯沙 (21至416 ng/g)、三氯卡班 (9至620 ng/g)及十二烷基二甲基苄基氯化銨 (167至6865 ng/g)。本研究中發現傳統污水廠無法有效去除部分的PCPs,未來有必要關注這類新興物質,並尋求更有效的污水處理方法。另外廢棄污泥中亦存在PCPs,若污泥有再利用之規劃,則有需要謹慎評估其對土壤環境及生物之影響。

    Personal care products (PCPs) are widely added to daily commodities. These substances and their derivatives may enter the domestic sewage treatment plants through the sanitary sewers since they are used in large quantities. Therefore, it is necessary to conduct a cautious assessment to ensure their ecological safety. In this study, four recombinant yeast bioassays were used to detect androgen receptor (AR), estrogen receptor (ER), mineralocorticoid receptor (MR) and progesterone receptor (PR) agonist/antagonist activities of domestic wastewater treatment plant (WWTP) samples and 18 target PCPs. Liquid chromatography tandem mass spectrometry (LC-MS/MS) was used to analyze the concentrations of 8 benzophenones (BPs), 6 parabens, 2 antimicrobials and 2 disinfectants in WWTP samples. The chlorinated derivatives of 2-hydroxy-4-methoxy-benzophenone (BP3), 5-chloro-2-hydroxybenzophenone (BP7) and 2,2'-dihydroxy-4-methoxy-benzophenone (BP8) were also identified in this study, and their endocrine disrupting activities were examined as well. Our results showed that BPs are potential endocrine disrupting chemicals, which exhibited AR antagonist, ER agonist/antagonist, MR antagonist and PR antagonist activities. In addition, their chlorinated derivatives also showed AR antagonist, ER antagonist, MR antagonist and PR antagonist activities. WWTP effluent samples exhibited MR antagonist activities, indicating that MR antagonistic chemicals were discharged into the environment. LC-MS/MS results revealed that the total concentrations of BPs ranged from 94 ng/L to 420 ng/L in effluent samples. The concentration of BAC-12 in sludge samples were up to μg/g levels. Our study suggested that it is necessary to pay more attention to PCPs in environment.

    摘要 I 誌謝 VI 目錄 VII 表目錄 XIII 圖目錄 XV 第一章 前言 1 1-1 研究動機 1 1-2 研究目的 2 第二章 文獻回顧 3 2-1 內分泌干擾物質 3 2-1-1 類(抗)雄激素物質 3 2-1-2 類(抗)雌激素物質 4 2-1-3 類(抗)鹽皮質激素物質 4 2-1-4 類(抗)孕激素物質 5 2-2 個人保健用品 6 2-2-1 防曬劑 6 2-2-2 防腐劑 7 2-2-3 抗菌劑 7 2-2-4 消毒劑 8 2-3 生物試驗法 12 2-3-1 活體內生物試驗法 12 2-3-2 活體外生物試驗法 12 2-4 儀器分析法 13 2-4-1 層析系統 13 2-4-2 偵測系統 13 2-5 檢測污水廠之簡介 14 2-5-1 桃園TB水資源回收中心 14 2-5-2 臺中FT水資源回收中心 15 2-5-3 臺南AN水資源回收中心 15 2-5-4 高雄FS水資源回收中心 15 第三章 實驗方法與步驟 16 3-1 實驗流程 16 3-2 樣本採集 18 3-3 實驗材料及設備 20 3-2-1 藥品與試劑 20 3-3-2 基因重組酵母菌試驗 22 3-4 樣本前處理 25 3-3-3 實驗設備 25 3-4-1 水相樣本 26 3-4-2 懸浮固相樣本 26 3-4-3 污泥樣本 27 3-4-4 樣本稀釋序列 27 3-5 報導基因重組酵母菌試驗法 28 3-5-1 類(抗)雄激素活性試驗 28 3-5-2 類(抗)雌激素活性試驗 29 3-5-3 類(抗)鹽皮質激素活性試驗 30 3-5-4 類(抗)孕激素活性試驗 31 3-5-5 生物試驗活性計算方法 34 3-6 儀器分析 36 3-6-1 液相層析串聯式質譜儀 36 3-6-2 回收率及偵測極限 40 3-7 二苯甲酮類防曬劑之氯化衍生物 42 3-7-1 衍生物之氯化合成與純化 42 3-7-2 高效液相層析儀 43 3-7-3 氯化衍生物之鑑定 44 3-7-4 生態毒性評估 44 3-8 風險商數之計算 45 3-9 生物試驗與儀器分析結果之相關性 46 第四章 結果與討論 48 4-1 目標物質之內分泌干擾活性 48 4-1-1 類(抗)雄激素活性 48 4-1-2 類(抗)雌激素活性 50 4-1-3 類(抗)鹽皮質激素活性 52 4-1-4 類(抗)孕激素活性 54 4-2 污水廠樣本之內分泌干擾活性 56 4-2-1 污水廠樣本之類(抗)雄激素活性 56 4-2-2 污水廠樣本之類(抗)雌激素活性 56 4-2-3 污水廠樣本之類(抗)鹽皮質激素活性 57 4-2-4 污水廠樣本之類(抗)孕激素活性 59 4-2-5 水相與懸浮固相樣本之抗鹽皮質激素活性分布 61 4-2-6 不同處理單元之抗鹽皮質激素活性綜合比較 62 4-2-7 污水廠平均每日排放之抗鹽皮質激素活性綜合比較 65 4-3 防曬劑於污水處理流程中之濃度變化 67 4-3-1 污水廠樣本中BP濃度變化 67 4-3-2 污水廠樣本中BP1濃度變化 69 4-3-3 污水廠樣本中BP2濃度變化 70 4-3-4 污水廠樣本中BP3濃度變化 71 4-3-5 污水廠樣本中BP4濃度變化 72 4-3-6 污水廠樣本中BP6濃度變化 74 4-3-7 污水廠樣本中BP7濃度變化 75 4-3-8 污水廠樣本中BP8濃度變化 76 4-3-9 污水廠樣本中總BPs濃度 77 4-4 防腐劑於污水處理流程中之濃度變化 80 4-4-1 污水廠樣本中MeP濃度變化 80 4-4-2 污水廠樣本中CMeP濃度變化 81 4-4-3 污水廠樣本中DCMeP濃度變化 82 4-4-4 污水廠樣本中EtP濃度變化 84 4-4-5 污水廠樣本中PrP濃度變化 85 4-4-6 污水廠樣本中BuP濃度變化 86 4-4-7 污水廠樣本中總Parabens濃度變化 87 4-5 抗菌劑於污水處理流程中之濃度變化 90 4-5-1 污水廠樣本中TCS濃度變化 90 4-5-2 污水廠樣本中TCC濃度變化 93 4-6 消毒劑於污水處理流程中之濃度變化 96 4-6-1 污水廠樣本中BAC-12濃度變化 96 4-7 二苯甲酮類防曬劑之氯化衍生物 99 4-7-1 氯化衍生物之鑑定 99 4-7-2 氯化BP3之內分泌干擾活性 103 4-7-3 氯化BP7之內分泌干擾活性 104 4-7-4 氯化BP8之內分泌干擾活性 105 4-7-5 氯化衍生物之毒性終點比較 106 4-8 氯化衍生物於污水廠放流水之檢測 108 4-9 風險商數 110 4-10 生物試驗與儀器分析相關性 112 第五章 結論與建議 115 5-1 結論 115 5-2 建議 117 參考文獻 118 附錄 132

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