甘草(licorice)為一般常用之中藥材,具有解毒、鎮痛、解痙、矯味、鎮咳袪痰等功效,且為食品加工業之添加物,但經人體食用後,仍會以原型態(parent compound)或代謝產物(metabilites)排泄出,並進一步流入環境水體。故此,本研究以甘草酸(glycyrrhizin)與甘草次酸(glycyrrhetic acid)為目標化合物,並以固相萃取法(solid phase extraction, SPE)搭配高效能液相層析串聯式質譜儀(high performance liquid chromatography tandem mass spectrometry, HPLC-MS/MS)建立目標化合物於環境水體中之分析方法,再利用此分析方法調查目標化合物於新店溪水樣及二家醫院放流水的流佈情形。 於SPE萃取方法方面,選用Oasis MCX 固相萃取管柱(cartridges),以6mL 甲醇流洗後再以6 mL 去離子水(DI water)活化萃取管柱,首先利用鹽酸將水樣調整至pH 2,水樣流經萃取管柱後,再以6 mL甲醇-氨水(95:5, v/v)之沖提液將萃取管柱中之目標化合物沖提,接著使用氮氣於37 ℃ 下將沖提液吹乾,最後再以400μL之甲醇-水(25:75, v/v)溶液回溶,可得最佳之萃取效果。另利用上述之SPE萃取方法進行不同基質(去離子水(DI water)、河川、醫院放流水)之回收率(理論添加濃度為100 ng/L)測試,回收率範圍均介於95-103%之間。方法偵測極限(S/N > 10)測試結果,甘草酸與甘草次酸於DI water中皆為10 ng/L,河川水樣中分別為10 ng/L和50 ng/L,於醫院水樣中則分別為20 ng/L及200 ng/L。 環境流佈調查結果,甘草酸與甘草次酸於新店溪中之濃度分佈範圍分別為11-82與77-327 ng/L;被檢出頻率分別為83及67%。於醫院出流水樣中,測得甘草酸及甘草次酸之濃度範圍分別為1443-1750 ng/L與226-7737 ng/L。
Licorice is one of common traditional Chinese medicines. Glycyrrhizin (GLY), the principle active ingredient of licorice, is the ingredient of antitussive and mucolytic-expectorant for the treatment of chronic hepatitis or allergies. GLY has also been widely used in food additives industry. After oral administration, GLY and its metabolite glycyrrhetic acid (GA) enter the aquatic environment via septic systems. The aims of this research were to: 1) develop analytical method of GLY and GA based on a solid phase extraction (SPE) procedure followed by liquid chromatography tandem mass spectroscopy and 2) investigate GLY and GA in Sindian river and two hospital effluents. In this research, the optimized SPE procedure that used Oasis MCX cartridges were pre-conditioned by rinsing with 6 mL methanol (MeOH) and 6 mL deionized water (DI water). After the conditioning step, water samples were percolated through MCX cartridges. Water samples were adjusted at pH 2 with hydrochloric acid. Then, the elute solution selected 6mL MeOH-NH4OH (95:5, v/v). Finally, the extract solutions are complete evaporated by nitrogen gas at 37 °C and reconstituted to 400 μL by MeOH-DI water (25:75, v/v). All standards were spiked at a concentration 100 ng/L into DI water and blank water samples. Recoveries ranged from 95-103% for DI water, river and hospital effluents by using the optimized SPE method. The method detection limits (MDLs) defined by signal-to-noise ratio of at least 10:1. MDLs of GLY and GA were 10 ng/L in DI water. MDLs varied between GLY and GA and were 10 ng/L and 50 ng/L for surface water, and 20 ng/L and 200 ng/L for hospital effluents, respectively. The result indicated the ubiquitous occurrence of GLY and GA in Sindian river. The detected concentration of GLY and GA ranged from 11 to 82 ng/L and 77 to 327 ng/L in Sindian river, respectively. The detected frequency of GLY and GA was 83% and 67%. The detected concentration of GLY and GA in hospital ranged from 1443 to 1750 ng/L and 226 to 7737 ng/L, respectively
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