Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece.
Anal Bioanal Chem. 2019 Mar;411(7):1383-1396. doi: 10.1007/s00216-018-01570-8. Epub 2019 Jan 9.
This work reports on a rapid and sensitive analytical method intended to be used for investigation of 25 multiclass pharmaceuticals in sediments. The method comprises a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction, followed by ultra-high-performance liquid chromatography-high-resolution linear ion trap/Orbitrap mass spectrometry, operated in positive ionization mode. The crucial parameters of both extraction and cleanup as well as those related to liquid chromatography and mass spectrometry were optimized and the method was validated in terms of accuracy, method detection and quantification limits, precision, linearity, and matrix effects. A matrix-matched calibration approach and isotopically labeled internal standards were employed for quantification and correction of matrix effects. In the optimized method, recoveries were calculated to be between 64 and 101% in the intermediate spiking level, with a relative standard deviation below 14%. Method quantification limits ranged from 1.3 to 47 ng g. The linearity, expressed as a correlation coefficient, was over 0.998 in all cases, within a range from each compound's method quantification limit to 250 ng g. The matrix effect study revealed slight signal suppression that decreased after the cleanup step for 50% of the pharmaceuticals, proving its adequacy to limit matrix interferences, without causing any important loss of relevant analytes. The applicability of the method was successfully tested in sediments from two Greek rivers in northwestern Greece, revealing the presence of paracetamol, risperidone, venlafaxine, citalopram, and carbamazepine and estimating for the first time the potential occurrence of pharmaceuticals in these two aquatic systems.
本工作报道了一种快速灵敏的分析方法，旨在用于研究沉积物中 25 种多类药物。该方法包括改良的快速、简便、廉价、有效、耐用和安全（QuEChERS）提取，随后进行超高效液相色谱-高分辨率线性离子阱/轨道阱质谱分析，采用正离子化模式。对提取和净化的关键参数以及与液相色谱和质谱相关的参数进行了优化，并对该方法进行了准确度、方法检测限和定量限、精密度、线性和基质效应的验证。采用基质匹配校准方法和同位素标记内标进行定量和校正基质效应。在优化的方法中，在中间加标水平下，回收率计算在 64%至 101%之间，相对标准偏差低于 14%。方法定量限范围为 1.3 至 47ng/g。在所有情况下，线性度（以相关系数表示）均大于 0.998，范围从每种化合物的方法定量限到 250ng/g。基质效应研究表明，50%的药物经过净化步骤后，信号略有抑制，表明其足以限制基质干扰，而不会导致任何重要的相关分析物损失。该方法的适用性已成功应用于希腊西北部两条希腊河流的沉积物中，揭示了扑热息痛、利培酮、文拉法辛、西酞普兰和卡马西平的存在，并首次估计了这些两个水系统中药物的潜在存在。
