本研究利用基因重組酵母菌生物試驗法搭配液相層析串聯式質譜儀，檢測臺灣五條河川水相及懸浮固體相之類(抗)雌激素活性及類(抗)雄激素活性於2012~2013年間之分布情形。採樣地點由北到南分別為淡水河、鹽水溪、二仁溪、阿公店溪及高屏溪。
生物試驗法結果顯示在二仁溪流域 (鯽潭橋、永寧橋和通地溝)及阿公店溪流域 (阿公店溪橋)之水相樣本具高類雌激素活性 (ND~71.2 E2-EQ ng/L)；懸浮固體樣本僅於鹽水溪流域 (千鳥橋)測得類雌激素活性 (13.8 E2-EQ ng/L)，其餘皆無明顯之類雌激素活性。各流域採樣點當中，無論水相或懸浮固體相大都具有抗雌激素活性 (ND~1222.6及ND~789.6 OHT-EQ μg/L)，顯示抗雌激素常存於河川水體當中。所有河川水相及懸浮固體相樣本皆無測得類雄激素活性。而在各流域採樣點之水相及懸浮固體大都具有抗雄激素活性 (ND~3377.5及ND~7869.3 FLU-EQ μg/L)，顯示抗雄激素亦常存於河川水體當中。
液相層析串聯式質譜儀分析結果顯示，5條河川之水相及懸浮固體相皆存在高濃度之雙酚A (ND~224.8 μg/L及ND~83.3 μg/L)及壬基酚 (76.0 ng/L~33.0 μg/L及ND~4265.0 ng/L)，並以二仁溪流域具有較高濃度的雙酚A和壬基酚。河川水相樣本中天然雌激素雌酮、雌二醇及雌三醇在淡水河流域 (ND~119.4 ng/L、ND及ND~64.8 ng/L)、鹽水溪流域 (ND~127.1 ng/L、ND~28.9 ng/L及ND~22.5 ng/L)、二仁溪流域 (14.3~225.6 ng/L、ND~26.4 ng/L及ND~408.3 ng/L)、阿公店溪流域 (17.7~154.6 ng/L、ND~33.6 ng/L及ND~142.1 ng/L)與高屏溪流域 (ND~304.1 ng/L、ND~108.3 ng/L及ND~78.5 ng/L)中皆有發現。河川之懸浮固體相中天然雌激素雌酮及雌三醇濃度較低 (ND~16.6 ng/L及ND~71.6 ng/L )，雌二醇 (ND~36.4 ng/L)出現的樣本數也較少，顯示天然雌激素不易存在於懸浮固體相中。由生物試驗法及儀器分析結果看來，生物試驗法測得之類雌/雄激素可能會受到水體中其他物質的拮抗作用使得活性下降，此外，目前所知的抗雌/雄激素物質對生物試驗活性的貢獻度很低 (<10%)，推測是環境樣品較為複雜，不同物質間可能會有拮抗的效應，或者是存在未知之抗雌/雄激素物質，還需進一步研究。

In this study, we used recombined yeast bioassays in combination with LC-MS/MS to detect the (anti)estrogenic and (anti)androgenic activities of water and suspended solid (SS) samples in five Taiwanese rivers. Sampling sites from Northem to Southem Taiwan were Danshuei (DS), Yanshuei (YS), Erren (ER), Agondian (AGD), and Gaoping (GP) rivers.
Bioassay results showed that high estrogenic activity (ND~71.2 E2-EQ ng/L) was detected in ER and AGD river water samples, and only one SS sample from YS river elicited estrogenic activity (13.8 E2-EQ ng/L). Most water and SS samples showed anti-estrogenic (ND~1222.6 and ND~789.6 OHT-EQ μg/L) and anti-androgenic (ND~3377.5 and ND~7869.3 FLU-EQ μg/L) activities. However, there was no androgenic activity in all of the samples.
LC-MS/MS analysis suggested that water and SS samples showed high concentrations of bisphenol A (ND~224.8 μg/L and ND~83.3 μg/L) and nonylphenol (76.0 ng/L~33.0 μg/L and ND~4265.0 ng/L). ER river had higher BPA an NP concentration than others. Estrone, estradiol, estriol were found in DS river (ND~119.4 ng/L, ND and ND~64.8 ng/L), YS river ((ND~127.1 ng/L, ND~28.9 ng/L and ND~22.5 ng/L), ER river (14.3~225.6 ng/L, ND~26.4 ng/L and ND~408.3 ng/L), AGD river (17.7~154.6 ng/L, ND~33.6 ng/L and ND~142.1 ng/L), and GP river (ND~304.1 ng/L, ND~108.3 ng/L and ND~78.5 ng/L) water samples. Lower concentrations of estrone (ND~16.6 ng/L) and estriol (ND~71.6 ng/L) were found in SS samples, and estradiol was found only in few samples (ND~36.4 ng/L), showing that natural estrogens seldom existed in the particulate phase. According to the bioassay results and the LC-MS/MS results, the known estrogenic/anti-androgenic compounds showed low contribution to the estrogenic/anti-androgenic activities detected by bioassays (<10%), which might be caused by the antagonists or unknown compounds in the complex water samples.

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