以快速固相萃取搭配極致液相層析/串聯式質譜儀分析水體中之管制藥品及其代謝物

Determination of Illicit Drugs and Their Metabolites in Water Using Fast Solid-phase Extraction and Ultra-performance Liquid Chromatography/Tandem Mass Spectrometry

馮鈺婷(Yu-Ting Feng)

指導教授 ： 陳家揚

國立臺灣大學/公共衛生學院/環境衛生研究所/碩士(2009年)

https://doi.org/10.6342/NTU.2009.03305

摘要

近年來，藥物（包括管制藥品）在環境的殘留是一逐漸被重視的議題。有些具活性之管制藥品或其代謝物可能無法被汙水處理廠降解，轉而進入環境中。這些藥物的殘留可能對環境或生態系統造成影響。
本研究開發圓盤型吸附劑快速萃取大體積水樣，利用極致液相層析搭配三段四極棒串聯式質譜儀、配合同位素稀釋技術精確定量環境水體中五種鴉片類與代謝物、五種安非他命類、三種氟硝西泮和代謝物以及五種古柯和代謝物等共18種化合物之檢驗方法。在經過前處理後，利用極致液相層析/串聯式質譜儀只需7.5分鐘即分離18種待測藥物並完成管柱再平衡，大幅縮短檢測所需時間並改善靈敏度。
本研究評估了電灑游離及大氣壓光游離法對於河水中待測藥物之基質效應，發現大氣壓光游離法的離子抑制較嚴重，尤其對於嗎啡尿苷酸(morphine-3β-D-glucuronide) 及芽子鹼甲酯 (ecgonine methyl ester) 影響最大，因此選擇電灑游離為分析生活汙水樣本之游離源。本研究量測待測藥物於台北市生活汙水廠之進流水及放流水之殘留量，瞭解化合物本體、代謝物之移除情形，並配合生活污水處理量和流域人口數的資訊推估台北市管制藥品之使用量。
以電灑游離作為游離源時，待測物在河水、進流水及放流水中之定量極限分別為0.054-8.76 ng/L、0.14-23.8 ng/L及0.22-15.2 ng/L。在廢水分析方面，約有一半的代謝物在進流水及放流水中皆可測得，包含可待因、甲基安非他命、搖頭丸、3,4-亞甲基雙氧安非他命、古柯鹼及其代謝物芽子鹼甲酯，顯示汙水處理廠未能完全去除這些管制藥物。在評估汙水廠服務範圍之管制藥品使用情形，發現兩水廠每天分別處理2-52克及5-226克的多種管制藥品 (包含海洛因、安非他命、甲基安非他命、搖頭丸及古柯鹼)；劑量分析方面，則以甲基安非他命使用劑量最高，估計15-64歲的族群每千人每日使用2個劑量(一劑以100 mg計算)。

關鍵字

管制藥物 ； 極致液相層析/串聯式質譜儀 ； 固相萃取 ； 廢水處理 ； 生活汙水 ； 電灑游離 ； 大氣壓光游離

並列摘要

Pharmaceuticals and personal care products in the environment, including illicit drugs residues, have become a public concern in recent years. Some of active illicit drugs or their metabolites may resist degradation in sewage treatment plants and enter the environment. The residues could affect the environment and the ecological system.
This study developed a method to rapidly extract a large volume of water using solid-phase extraction disks and utilized ultra-performance liquid chromatography (UPLC) combined with triple-quadrupole mass spectrometer and isotope-dilution techniques to determine several types of illicit drugs, including opiates, amphetamines, flunitrazepam, heroin and their metabolites in water. After sample pretreatment, chromatographic separation of the 18 drugs can be done in 7.5 minutes (including re-equilibrium), and the sensitivity as well as sample throughput were much improved.
This study compared the sensitivity and matrix effects in river water between electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). The later was found to be more susceptible to matrix effects, especially for morphine-3β-D-glucuronide and ecgonine methyl ester. For this reason, ESI was selected to ionize analytes in sewage samples. This study also determined the residues of illicit drugs and their metabolites in influents and effluents of Taipei sewage treatment plants (STPs) and evaluated the removal efficiency on these chemicals. The consumption of illicit drugs in Taipei was also estimated based on the population in the served area, based on flows of the STPs and measured levels of these chemicals in the influents.
In ESI mode, LOQs for illicit drugs in river water, influents and effluents were 0.054-8.76 ng/L, 0.14-23.8 ng/L and 0.22-15.2 ng/L, respectively. About half of the analytes were detected in both influents and effluents, including codeine, methamphetamine, MDMA, MDA, cocaine and its metabolite ecgonine methyl ester, which revealed that these chemicals could not be completely removed by STPs. The two STPs carried the equivalent of 2 to 52 g and 5 to 226 g of detected illicit drugs (including heroin, amphetamine, methamphetamine, MDMA and cocaine) per day. The consumption of methamphetamine was the highest among all the illicit drugs. At least two doses (100 mg per dose) were consumed per day per thousand people aged between 15 and 64 years.

並列關鍵字

illicit drugs ； UPLC/MS/MS ； solid-phase extraction ； waste water treatment ； sewage ； electrospray ionization ； atmospheric pressure photoionization

參考文獻

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