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研究生: 吳品錡
Wu, Pin-Chi
論文名稱: 污水處理廠中有機磷酸三酯及有機磷酸二酯的濃度變化與內分泌干擾活性探討
Occurrence of organophosphate triesters and diesters in wastewater treatment plants and their endocrine disrupting activities
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: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 119
中文關鍵詞: 污水處理廠有機磷阻燃劑有機磷酸三酯有機磷酸二酯液相層析串聯式質譜儀內分泌干擾活性
外文關鍵詞: organophosphorus flame retardants, organophosphate triesters, organophosphate diesters, liquid chromatography tandem mass spectrometry, endocrine disrupting chemicals, yeast-based reporter gene assays
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  • 阻燃劑為一種添加至產品中來降低可燃性以防止火災的蔓延的化學藥劑。過往主要使用之溴化阻燃劑如多溴二苯醚 (Polybrominated diphenyl ethers, PBDEs),已因其毒性及生物危害而逐漸被禁止生產和使用。近年來,取代溴化阻燃劑的有機磷阻燃劑 (Organophosphate flame retardants, OPFRs)已廣泛應用於工業及民生用品中,然而,目前亦發現OPFRs具有神經毒性、生殖毒性及內分泌干擾活性。作為有機磷酸三酯阻燃劑的主要降解產物,有機磷酸二酯也隨之受到重視,研究顯示有機磷酸二酯也具有生殖毒性、發育毒性,並可能會影響內分泌系統。當這些物質無法被污水處理程序有效去除時,則會隨著放流水排放至自然水體,因此有必要了解其在污水處理程序中的濃度變化。
    本研究採集臺灣四座民生污水廠各個處理單元之出流水及廢棄污泥,選擇常見之11種有機磷酸三酯及8種有機磷酸二酯作為目標物質,以報導基因酵母菌試驗法檢測目標物質及污水廠樣本之內分泌干擾活性,並使用液相層析串聯質譜儀分析目標物質於樣本之濃度。內分泌干擾活性試驗結果顯示有機磷酸三酯大多具有抗鹽皮質激素、抗糖皮質激素活性以及抗孕激素活性,然而多數有機磷酸二酯則不具類(抗)鹽皮質激素、類(抗)糖皮質激素活性和類(抗)孕激素活性,僅二(2-乙基己基)磷酸酯具有抗糖皮質激素和抗鹽皮質激素活性。此外,污水廠放流水樣本仍可測得抗鹽皮質激素與抗糖皮質激素活性,而污泥樣本測得抗鹽皮質激素和抗孕激素活性,表示這些內分泌干擾物質會進到自然水體中。
    液相層析串聯質譜儀的結果顯示在各污水廠進流中測得9種有機磷酸三酯和7種有機磷酸二酯,總有機磷酸三酯濃度範圍為644.4至1692.6 ng/L;總有機磷酸二酯濃度範圍為642.2至2290.1 ng/L,其中有機磷酸三酯以磷酸三(2-丁氧基乙基)酯、磷酸三正丁酯和三(氯異丙基)磷酸酯為主要物質,而有機磷酸二酯以磷酸二甲酯、鄰苯二甲酸二(2-丁氧基)乙酯和二(2-乙基己基)磷酸酯為主要物質。在各污水廠放流水中測得總有機磷酸三酯和二酯濃度範圍為298.3至1103.5 ng/L和9.1至53.9 ng/L,與進流相比濃度有明顯下降,值得一提的是有機磷酸三酯的去除率可因其官能基的不同有明顯的差異,研究結果顯示烷基有機磷酸三酯的去除率為49.2至100 %,氯化和芳香基有機磷酸三酯的去除率為-35.6至68.7 %,表明傳統污水處理程序針對氯化和芳香基有機磷酸三酯去除率不佳。於污泥樣本中也可測得有機磷酸三酯與二酯濃度範分別是7.3至596.1 ng/g和1.0至212.0 ng/g。本研究中發現在放流水樣本中仍可測得部份有機磷酸三酯與二酯,未來有必要持續關注這些物質,並謹慎評估其對水生環境及生物的影響。另外,在污泥仍存在有機磷酸酯,若有污泥再利用,需評估其對土壤生物的影響。

    In recent years, due to the gradual restriction of the use of polybrominated diphenyl ethers (PBDEs), organophosphate triesters (OP triesters) have become suitable substitutes and are widely used as flame retardants and plasticizers in plastics, textiles, electronics, etc. OP triesters have been previously reported in various environmental samples, such as surface water, wastewater, sediment, and air. In addition, many studies showed that OP triesters have neurotoxic, carcinogenic, and endocrine disrupting activities. As the main degradation products of OP triesters, organophosphate diesters (OP diesters) have also gradually attracted attention.
    In this study, liquid chromatography tandem mass spectrometry (LC-MS/MS) was used to analyze the concentrations of the 11 OP triesters and 8 OP diesters in wastewater treatment plants (WWTPs). Our results showed that 9 OP triesters were detected in WWTPs effluents, and tributyl phosphate (TnBP), tris(2-butoxyethyl) phosphate (TBEP), and tris(chloroisopropyl) phosphate (TCPP) identified as the dominant compounds. The total concentrations of OP triesters ranged from 298.3 to 1103.5 ng/L. In addition, 7 OP diesters were also detected in WWTPs effluents, and the concentrations of total OP diesters ranged from 9.1 to 53.9 ng/L. Bioassay results showed that OP triesters are potential EDCs, in particular, chlorinated and aryl-OP triesters exhibited strong anti-mineralocorticoid and anti-glucocorticoid activities. OP triester and OP diester concentrations were also detected in the sludge samples ranging from 7.3 to 596.1 ng/g and 1.0 to 212.0 ng/g, respectively. Moreover, anti-mineralocorticoid and anti-glucocorticoid activities were also found in WWTPs effluents, indicating that anti-mineralocorticoid and anti-glucocorticoid chemicals may be spread into the environment. Our study suggested that it is necessary to pay more attention to OP triesters and OP diesters discharged into environment.

    摘要I 致謝IX 目錄X 表目錄XIV 圖目錄XVI 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)雌激素物質3 2-1-2 類(抗)甲狀腺激素物質4 2-1-3 類(抗)糖皮質激素物質4 2-1-4 類(抗)鹽皮質激素物質5 2-1-5 類(抗)孕激素物質6 2-1-6 類芳香烴物質6 2-2 有機磷阻燃劑7 2-2-1 有機磷酸三酯之危害與特性7 2-2-2 有機磷酸二酯之危害與特性12 2-3 生物試驗法16 2-3-1 活體內生物試驗16 2-3-2 活體外生物試驗16 2-4 儀器分析方法17 2-4-1 層析系統17 2-4-2 偵測系統18 2-5 檢測污水廠之簡介18 2-5-1 桃園TB 水資源回收中心18 2-5-2 臺中FT 水資源回收中心18 2-5-3 臺南AP 水資源回收中心19 2-5-4 高雄FS 水資源回收中心19 第三章 實驗方法與步驟20 3-1 實驗材料及設備20 3-1-1 藥品與試劑20 3-1-2 實驗設備22 3-2 實驗流程23 3-3 樣本採集24 3-4 樣本前處理26 3-4-1 水相樣本26 3-4-2 懸浮固相樣本27 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28 3-5-1 類(抗)激素受體干擾試驗原理機制28 3-5-2 類(抗)激素活性計算35 3-6 儀器分析36 3-6-1 液相層析串聯質譜儀36 3-6-2 回收率及偵測極限41 3-7 風險商數之計算44 3-8 生物試驗與儀器分析結果之相關性45 第四章 結果與討論47 4-1 目標物質之內分泌干擾活性47 4-1-1 類(抗)甲狀腺激素活性48 4-1-2 類(抗)糖皮質激素活性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 4-1-5 有機磷酸三酯與二酯內分泌干擾活性比較56 4-2 污水廠樣本之內分泌干擾活性57 4-2-1 污水廠樣本之類(抗)甲狀腺激素活性57 4-2-2 污水廠樣本之類(抗)糖皮質激素活性57 4-2-3 污水廠樣本之類(抗)鹽皮質激素活性60 4-2-4 污水廠樣本之類(抗)孕激素活性63 4-3 有機磷酸三酯於污水廠中之濃度變化65 4-3-1 AP 污水廠中有機磷酸三酯之濃度變化65 4-3-2 FS 污水廠中有機磷酸三酯之濃度變化67 4-3-3 FT 污水廠中有機磷酸三酯之濃度變化69 4-3-4 TB 污水廠中有機磷酸三酯之濃度變化71 4-3-5 有機磷酸三酯於污水廠污泥樣本之濃度變化72 4-3-6 污水廠之有機磷酸三酯濃度綜合比較74 4-4 污水廠中有機磷酸二酯之濃度變化80 4-4-1 AP 污水廠中有機磷酸二酯之濃度變化80 4-4-2 FS 污水廠中有機磷酸二酯之濃度變化82 4-4-3 FT 污水廠中有機磷酸二酯之濃度變化84 4-4-4 TB 污水廠中有機磷酸二酯之濃度變化86 4-4-5 有機磷酸二酯於污水廠污泥樣本之濃度變化88 4-4-6 污水廠之有機磷酸二酯濃度綜合比較90 4-5 風險商數97 4-6 生物試驗與儀器分析結果之相關性98 第五章 結論與建議103 5-1 結論103 5-2 建議105 參考文獻106 附錄115

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