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研究生: 陳遠超
Chen, Yuan-Chao
論文名稱: 臺灣觀光海灘海水及沙灘中有機紫外線過濾劑之濃度分布及其內分泌干擾活性探討
Occurrence and distribution of organic UV filters in seawater and beach sand in 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: 138
中文關鍵詞: 海灘紫外線過濾劑報導基因生物試驗法內分泌干擾活性液相層析串聯式質譜儀
外文關鍵詞: Beach, UV filter, Yeast-based reporter gene assay, Endocrine-disrupting activity, Liquid chromatography-tandem mass spectrometry
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  • 隨著工業和技術的發展,有越來越多種化學物質被廣泛地添加於個人保健用品之中,這些物質為人們帶來便利的同時,也透過各種管道進入環境。有機紫外線過濾劑常被添加至防曬乳及乳液等化妝品內,而這些紫外線過濾劑是水體中的新興污染物之一,當我們在海邊活動時其會流入至環境中,使得水生環境受到危害。
    本研究採集臺灣北部及南部地區之觀光海灘之海水樣本以及沙子樣本,使用報導基因重組酵母菌試驗法檢測紫外線過濾劑及各樣本之內分泌干擾活性,亦利用液相層析串聯式質譜儀分析目標物質之環境濃度。內分泌干擾活性試驗結果顯示紫外線過濾劑中大多具有抗雄激素活性、抗糖皮質激素活性、抗鹽皮質激素活性、抗孕激素活性以及類芳香烴活性。抗雄激素活性、抗雌激素活性、抗鹽皮質激素活性以及類芳香烴活性可於海水樣本中測得;類芳香烴活性也可於沙子樣本中測得。
    液相層析串聯式質譜儀分析結果顯示海水中檢測到最高濃度之物質為 2-羥基-4甲氧基二苯甲酮 (2-Hydroxy-4-methoxybenzophenone, BP3) (597.4 ng/L),於懸浮固相樣本中檢測到最高濃度物質為奧克立林 (Octocrylene, OC) (71.6 ng/L),於沙子樣本中檢測到最高濃度之物質為水楊酸辛酯 (2-Ethylhexyl salicylate, ES) (27.0 ng/g sand dw)。
    以風險商數評估各海水樣本中紫外線過濾劑的生態風險後,確認大部分的目標紫外線過濾劑不具生態風險,僅有於夏季福隆海水浴場 (FL-S) 測得之BP3具有高度風險 (風險商數大於 1.0),於夏季金沙灣海濱公園 (JS-S)及夏季漁光島沙灘 (YI-S)測得之2,4-二羥基二苯甲酮 (2,4-Dihydroxybenzophenone, BP1)、於 JS-S 測得之 BP3、及於FL-S測得之胡莫柳酯 (Homosalate, HS)、OC具有中度風險 (0.1<風險商數<1.0)。此外,經計算生物試驗與儀器分析結果之相關性,發現 BP3 於部分樣本之類芳香烴活性之貢獻度大於 10%,而其餘目標紫外線過濾劑並非樣本中內分泌干擾活性之主要貢獻來源。

    With the development of industry and technology, an increasing number of chemicals are being widely added to personal care products. While these substances bring convenience to people, they also enter the environment through various channels. Organic UV filters are commonly added to sunscreens and lotions, making them one of the emerging contaminants in aquatic environments. When we engage in activities at the beach, these UV filters can enter the environment, posing a threat to aquatic ecosystems.
    This study focused on tourist beaches in northern and southern Taiwan. Seawater and sand samples were collected from various sampling sites. The endocrine-disrupting activities of UV filters and the samples were detected using recombinant yeast assays, and the environmental concentrations of target substances were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results of the endocrine disrupting activity tests showed that most UV filters exhibited anti-androgenic, anti-glucocorticoid, anti-mineralocorticoid, anti-progestogenic, and aryl hydrocarbon receptor (AhR) agonist activities. Anti-androgenic, anti-estrogenic, anti-mineralocorticoid, and AhR agonist activities were detected in seawater samples. Sand samples exhibited AhR agonist activities as well.
    LC-MS/MS analysis results indicated that 2-hydroxy-4-methoxybenzophenone (BP3), octocrylene (OC), and 2-ethylhexyl salicylate (ES) were detected in seawater, suspended solids, and sand samples at the highest concentrations (597.4 ng/L, 71.6 ng/L, 27.0 ng/g sand dw), respectively.
    Ecological risk assessment of UV filters in seawater samples showed that most target UV filters posed no ecological risks, only BP3 at Fulong beach in summer (FL-S) showed a high risk (risk quotient > 1.0), 2,4-dihydroxybenzophenone (BP1) at Jinsha Bay beach park in summer (JS-S) and Yuguang Island beach in summer (YI-S), BP3 at JS-S and homosalate (HS), and OC at FL-S posed moderate risks (0.1 < risk quotient < 1.0). The correlation between bioassay results and instrumental analysis results were calculated as well. Except for BP3, which contributed to more than 10% of the AhR agonist activities in some samples, the other target UV filters were not the primary contributors to the endocrine-disrupting activities of the samples.

    摘要 I 誌謝 VIII 目錄 IX 表目錄 XIV 圖目錄 XVI 第一章 前言 19 1-1 研究動機 19 1-2 研究目的 19 第二章 文獻回顧 20 2-1 內分泌干擾物質 20 2-1-1 類(抗)雄激素物質 20 2-1-1-1 類雄激素物質 20 2-1-1-2 抗雄激素物質 21 2-1-2 類(抗)雌激素物質 22 2-1-2-1 類雌激素物質 22 2-1-2-2 抗雌激素物質 23 2-1-3 類(抗)鹽皮質激素物質 24 2-1-3-1 類鹽皮質激素物質 24 2-1-3-2 抗鹽皮質激素物質 25 2-1-4 類(抗)孕激素物質 25 2-1-4-1 類孕激素物質 25 2-1-4-2 抗孕激素物質 26 2-1-5 類(抗)甲狀腺激素物質 27 2-1-5-1 類甲狀腺激素物質 27 2-1-5-2 抗甲狀腺激素物質 27 2-1-6 類(抗)糖皮質激素物質 28 2-1-6-1 類糖皮質激素物質 28 2-1-6-2 抗糖皮質激素物質 29 2-1-7 類芳香烴物質 30 2-2 紫外線過濾劑 31 2-2-1 二苯甲酮類 31 2-2-2 水楊酸酯類 32 2-2-3 肉桂酸酯類 33 2-2-4 樟腦衍生物 33 2-3 生物試驗法 34 2-3-1 活體外生物試驗 36 2-3-2 活體內生物試驗 36 2-4 目標海灘之簡介 38 2-4-1 新北金沙灣海濱公園 38 2-4-2 新北福隆海水浴場 38 2-4-3 臺南四鯤鯓海岸 38 2-4-4 臺南漁光島沙灘 39 2-4-5 屏東墾丁大光沙灘 39 2-4-6 屏東墾丁南灣遊憩區 39 第三章 實驗方法與步驟 40 3-1 實驗流程 40 3-2 樣本採集 41 3-2-1 採樣方法 42 3-2-1-1 海水樣本 42 3-2-1-2 沙灘樣本 42 3-3 實驗材料及設備 44 3-3-1 藥品與試劑 44 3-3-2 實驗設備 46 3-4 樣本前處理 48 3-4-1 水相樣本 48 3-4-2 懸浮固相樣本 48 3-4-3 沙灘樣本 49 3-4-3-1 超音波萃取法 49 3-4-4 樣本稀釋序列 49 3-5 報導基因重組酵母菌試驗法 50 3-5-1 雄激素∕甲狀腺激素∕孕激素∕糖皮質激素∕鹽皮質激素受體干擾試驗原理 50 3-5-2 類芳香烴活性試驗原理 50 3-5-3 雌激素受體干擾試驗原理 51 3-5-4 類(抗)激素活性試驗 51 3-5-4-1 類(抗)雄激素活性試驗 51 3-5-4-2 類(抗)甲狀腺激素活性試驗 52 3-5-4-3 類(抗)孕激素活性試驗 53 3-5-4-4 類(抗)糖皮質激素活性試驗 53 3-5-4-5 類(抗)鹽皮質激素活性試驗 54 3-5-4-6 類芳香烴活性試驗 55 3-5-4-7 類(抗)雌激素活性試驗 58 3-5-5 生物試驗活性計算方法 61 3-5-5-1 類(抗)激素當量濃度換算 62 3-6 儀器分析 64 3-6-1 液相層析串聯式質譜儀 64 3-6-2 回收率及偵測極限 69 3-7 風險商數之計算 72 3-8 生物試驗與儀器分析結果之相關性 74 第四章 結果與討論 76 4-1 目標物質之內分泌干擾活性 76 4-1-1 類(抗)雄激素活性 76 4-1-2 類(抗)雌激素活性 78 4-1-3 類(抗)孕激素活性 80 4-1-4 類(抗)鹽皮質激素活性 82 4-1-5 類(抗)糖皮質激素活性 83 4-1-6 類(抗)甲狀腺激素活性 84 4-1-7 類芳香烴活性 85 4-1-8 目標物質之內分泌干擾活性整理 86 4-2 海水及懸浮固相樣本之內分泌干擾活性 87 4-2-1 海水及懸浮固相樣本之類(抗)雄激素活性 87 4-2-2 海水及懸浮固相樣本之類(抗)雌激素活性 88 4-2-3 海水及懸浮固相樣本之類(抗)孕激素活性 89 4-2-4 海水及懸浮固相樣本之類(抗)鹽皮質激素活性 89 4-2-5 海水及懸浮固相樣本之類(抗)糖皮質激素活性 90 4-2-6 海水及懸浮固相樣本之類(抗)甲狀腺激素活性 91 4-2-7 海水及懸浮固相樣本之類芳香烴活性 91 4-2-8 海水及懸浮固相樣本之各種內分泌干擾活性討論 92 4-3 海水及懸浮固相樣本之紫外線過濾劑濃度分析 94 4-3-1 海水樣本中紫外線過濾劑 94 4-3-2 懸浮固相樣本中紫外線過濾劑 100 4-3-3 懸浮固相樣本單位重之紫外線過濾劑 102 4-4 沙子樣本之內分泌干擾活性 103 4-4-1 沙子樣本之類(抗)激素活性 103 4-4-2 沙子樣本之類芳香烴活性 103 4-5 沙子樣本之紫外線過濾劑濃度分析 108 4-6 目標物質之風險評估及健康風險 113 4-7 生物試驗與儀器分析相關性 114 第五章 結論與建議 119 5-1 結論 119 5-2 建議 121 參考文獻 122 附錄 131

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