| 研究生: |
林力維 Lin, Li-Wei |
|---|---|
| 論文名稱: |
臺灣中南部河川中有機磷阻燃劑與其降解產物之分布及內分泌干擾活性探討 Occurrence of organophosphate triesters and their degradation products in rivers of central and southern Taiwan 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: | 2024 |
| 畢業學年度: | 112 |
| 語文別: | 中文 |
| 論文頁數: | 162 |
| 中文關鍵詞: | 河川 、有機磷阻燃劑 、有機磷酸酯代謝物 、液相層析串聯質譜儀 、內分泌干擾活性 |
| 外文關鍵詞: | Rivers, Organophosphate flame retardants, Organophosphate ester metabolites, Liquid chromatography-tandem mass spectrometry (LC-MS/MS), Endocrine disrupting activities |
| 相關次數: | 點閱:56 下載:0 |
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近年來,有機磷酸酯 (Organophosphate esters, OPEs) 逐漸取代多溴二苯醚成為主要的阻燃劑成分。有機磷阻燃劑常被添加至工業以及商業產品之中,目前已被證實會導致許多不同危害,如生殖毒性、神經毒性、發育毒性、致癌性以及對內分泌系統產生干擾。河川為接受放流水的主要自然水體,而污水排放為有機磷阻燃劑進入環境中的途徑之一。因此需要瞭解有機磷阻燃劑於環境中的宿命,以評估其對生態環境之風險。
本研究採集中、南部三條河川之樣本,並選擇有機磷酸三酯、有機磷酸二酯、有機磷酸酯羥基代謝物以及有機磷酸單酯作為目標物質,以報導基因重組酵母菌試驗檢測水相、懸浮固相、底泥及目標有機磷酸酯之類(抗)雄激素、類(抗)雌激素、類(抗)糖皮質激素、類(抗)鹽皮質激素、類(抗)孕激素、與類(抗)甲狀腺激素活性。此外,研究中使用液相層析串聯質譜儀分析有機磷酸阻燃劑及降解產物之環境濃度,以瞭解其於環境中之分布情形,並討探樣本中內分泌干擾活性與目標物質之相關性。
內分泌干擾活性試驗結果顯示,大部分有機磷酸三酯及少數有機磷酸羥基代謝物具有抗糖皮質激素活性、抗鹽皮質激素活性以及抗孕激素活性,而部分有機磷酸二酯具有抗糖皮質激素以及抗鹽皮質激素活性,有機磷酸單酯則無內分泌干擾活性。於河川水相中廣泛檢測出抗糖皮質激素、抗鹽皮質激素與類芳香烴活性,底泥中則廣泛檢測出類芳香烴活性,顯示具抗糖皮質激素、抗鹽皮質激素與類芳香烴活性存在於受測河川中。
液相層析串聯質譜儀的結果顯示在各條河川中測得10種有機磷酸三酯、6種有機磷酸二酯、及2種有機磷酸羥基化代謝物。有機磷酸三酯於乾、濕季水相樣本之總濃度範圍為10.16 – 2409.7 ng/L,懸浮固相為1.0 – 718.3 ng/L,底泥樣本則為0.1 – 50.1 ng/g。有機磷酸酯代謝物於乾濕季水相樣本之總濃度範圍則為0.2 – 521.8 ng/L,懸浮固相樣本為0.2 – 16.2 ng/L,底泥樣本為0.5 – 10.7 ng/g。其中水相樣本中主要測得之磷酸三(2-丁氧基乙基)酯 (Tris(2-butoxyethyl) phosphate, TBOEP)、三(1-氯-2-丙基)磷酸酯 (Tris(1-chloro-2-propyl) phosphate, TCPP)、三(1,3-二氯-2-丙基)磷酸酯 (Tris(1,3-dichloro-2-propyl) phosphate, TDCPP),及磷酸二苯酯 (Diphenyl phosphate, DPHP)、磷酸二丁酯 (Dibutyl phosphate, DnBP)、磷酸二(2-乙基己基)酯 (Bis(2-ethylhexyl) phosphate, BEHP)以及雙(2-丁氧基乙基)2-(3-羥基丁氧基)乙基磷酸三酯 (Bis(2-butoxyethyl) 2-(3-hydroxybutoxy)ethyl phosphate triester, 3-OH-TBOEP)。於懸浮固相中則主要檢測到磷酸三丁酯 (Tributyl phosphate, TnBP)、磷酸三(2-乙基己基)酯 (Tris(2-ethylhexyl) phosphate, TEHP)、3-羥丁基磷酸二丁酯 (Dibutyl-3-hydroxybutyl phosphate, 3-OH-TnBP)。於底泥中主要檢測出TCPP、TPPO、TEHP及DPHP。顯示有機磷酸酯會以不同的形式存在於環境之中。
生態風險評估的結果顯示,乾、濕季時之BEHP於多數採樣點之風險商數介於0.1與1之間,屬中度風險,並於北港溪上游處呈高度風險。此外,濕季時阿公店溪下游處之TBOEP與鹽水溪下游處之TnBP的風險商數介於0.1與1之間,屬中度風險。應持續監測河川中這些物質之污染來源與狀況以進一步減少其環境影響。
The increasing use of organophosphate esters (OPEs) as flame retardants has raised environmental concerns due to their potential endocrine-disrupting activities. This study investigated the occurrence and distribution of OPEs and their degradation products in the rivers of central and southern Taiwan and assessed their endocrine-disrupting activities. Environmental samples, such as water, suspended solids, and sediments were collected from three rivers in Taiwan. Endocrine disrupting activities of river samples were detected with recombinant yeast reporter gene assays, and target compounds including organophosphate tri-esters, di-esters, monoesters and hydroxylated organophosphate esters were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Our study revealed that glucocorticoid receptor (GR) antagonistic, mineralocorticoid receptor (MR) antagonistic and aryl hydrocarbon receptor (AhR) agonist activities were found in different matrices. In addition to the detection of organophosphate tri-esters, the presence of organophosphate di-esters and hydroxylated metabolites in environment was also observed. The results of risk assessment indicated that bis(2-ethylhexyl) phosphate (BEHP), tris(2-butoxyethyl) phosphate (TBOEP) and tributyl phosphate (TnBP) posed moderate to high risks, and continuous monitoring of river pollution is necessary.
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校內:2026-08-31公開