Determination of pharmaceuticals in freshwater sediments using ultrasonic-assisted extraction with SPE clean-up and HPLC-DAD or LC-ESI-MS/MS detection
Determination of pharmaceuticals in freshwater sediments using ultrasonic-assisted extraction with SPE clean-up and HPLC-DAD or LC-ESI-MS/MS detection
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DOI：
10.1039/c7ay00650k
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发表时间：
2017-07
影响因子：
3.1
通讯作者：
O. Al-Khazrajy;A. Boxall
中科院分区：
文献类型：
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作者：
O. Al-Khazrajy;A. Boxall
提出了一种稳健且灵敏的分析方法，用于淡水沉积物中六种药物的提取和测定。使用含2%氢氧化铵的甲醇（MeOH）超声提取沉积物中的药物，随后用含2%甲酸的MeOH以及仅用MeOH进行提取。所得提取物经HLB固相萃取柱净化后，使用Zorbax Eclipse XDB - C18（150×4.6 mm，5μm）柱以及由10 mM醋酸铵和MeOH（pH = 4.8）组成的流动相进行单次梯度洗脱分析。使用二极管阵列检测器（DAD）或正模式电喷雾电离串联质谱（MS/MS）对分析物进行检测和定量。使用从英国和伊拉克采集的十种具有广泛特性的沉积物进行了验证研究。在所有研究的沉积物中，强化样品的平均计算回收率为：阿替洛尔74.5% - 114.6%，阿米替林72.3% - 124.9%，甲芬那酸76.5% - 105%，地尔硫卓70.1% - 102%。西咪替丁和雷尼替丁的回收率较低，分别为40.2% - 68.4%和30.4% - 55.2%。所有沉积物 - 药物组合回收率的相对标准偏差（RSD）为1.6% - 15.8%。六种分析物在沉积物中的检测限分别为：高效液相色谱 - 紫外检测（HPLC - UV）15 - 58.5 ng g⁻¹，液相色谱 - 电喷雾电离串联质谱（LC - ESI - MS/MS）0.03 - 3.5 ng g⁻¹（干重）。总体而言，结果表明所开发的方法可有效用于监测不同地区水生沉积物中药物的浓度。
A robust and sensitive analytical method is presented for the extraction and determination of six pharmaceuticals in freshwater sediments. The pharmaceuticals were extracted from sediment using ultrasonic extraction with 2% NH4OH in methanol (MeOH), followed by extraction into 2% formic acid in MeOH and then MeOH only. The resulting extracts were then analysed, after clean-up on HLB solid phase extraction cartridges, using a single gradient run using a Zorbax Eclipse XDB-C18 (150 × 4.6 mm, 5 μm) column and a mobile phase consisting of 10 mM ammonium acetate and MeOH (pH = 4.8). Analytes were detected and quantified using either Diode Array Detector (DAD) or tandem mass spectrometry (MS/MS) with electrospray ionization in positive mode. Validation studies were carried out using ten sediments sampled from the UK and Iraq with a wide range of characteristics. The mean calculated recoveries for fortified samples in all studied sediments ranged from 74.5 to 114.6% for atenolol, 72.3 to 124.9% for amitriptyline, 76.5 to 105% for mefenamic acid and 70.1 to 102% for diltiazem. Cimetidine and ranitidine showed lower recoveries which ranged from 40.2 to 68.4% and 30.4 to 55.2% respectively. Relative standard deviations (RSD) of recoveries for all sediment–pharmaceutical combinations ranged from 1.6 to 15.8%. The detection limits in sediments for the six analytes ranged from 15 to 58.5 ng g−1 and 0.03 to 3.5 ng g−1, dry weight, for HPLC-UV and LC-ESI-MS/MS respectively. Overall the results indicate that the developed method is effective for use in monitoring the concentrations of pharmaceuticals in aquatic sediments in different regions.