Department of Chemistry and Physics, University of Almería, Campus de Excelencia Agroalimentario, ceiA3, La Cañada de San Urbano, 04120 Almería, Spain.
J Chromatogr A. 2013 May 24;1291:19-26. doi: 10.1016/j.chroma.2013.03.066. Epub 2013 Mar 29.
A simple, rapid, low environmental toxicity and sensitive ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of nine pharmaceuticals (paracetamol, metoprolol, bisoprolol, betaxolol, ketoprofen, naproxen, ibuprofen, flufenamic acid and tolfenamic acid) in wastewater, and their determination using high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS). The IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and acetonitrile (ACN) were used as extraction and disperser solvent, respectively, for the DLLME procedure, instead of using toxic chlorinated solvent. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.5mL of acetonitrile), which increased the extraction efficiency and reduced the equilibrium time. A slight increase in the recoveries of pharmaceuticals was observed when an ice-water bath extraction step was included in the analytical procedure. In this way, enrichment factors between 255 and 340 were obtained. Data acquisition in selected reaction monitoring mode (SRM), allowed the simultaneous identification and quantification of the analytes using two transitions (SRM1 and SRM2). Additionally, the information dependent acquisition (IDA) scan was performed to carry out the identification of those analytes whose second transition was absent or was present at low intensity, also providing extra confirmation for the other analytes. The optimized US-IL-DLLME-LC-QqLIT-MS method showed a good precision level, with relative standard deviation values between 1.1% and 11.3%. Limits of detection and quantification were in the range 0.2-60ngL(-1) and 1.0-142ngL(-1), respectively. Good enrichment factors (255-340) and recoveries (88-111%) were obtained for the extraction of the target analytes in wastewater samples. This method has been successfully applied to analyze effluent wastewater samples from a municipal wastewater treatment plant located in Almería (Spain) and the results indicated the presence of flufenamic acid and metoprolol in concentration levels of 0.1 and 1.3μgL(-1), respectively.
一种简单、快速、低环境毒性和灵敏的超声辅助离子液体分散液液微萃取（US-IL-DLLME）程序被开发用于从废水中提取九种药物（对乙酰氨基酚、美托洛尔、比索洛尔、倍他洛尔、酮洛芬、萘普生、布洛芬、氟芬那酸和托芬那酸），并使用高效液相色谱-混合三重四极杆-线性离子阱-质谱联用仪（LC-QqLIT-MS）进行测定。IL 1-辛基-3-甲基咪唑六氟磷酸盐（[C8MIM][PF6]）和乙腈（ACN）分别用作萃取和分散溶剂，用于 DLLME 程序，而不是使用有毒的氯化溶剂。优化了影响萃取效率的因素，如离子液体的类型和体积、分散溶剂的类型和体积、冰水冷却、超声时间、离心时间、样品 pH 值和离子强度。超声辅助过程用于加速使用小体积分散溶剂（0.5mL 乙腈）形成细云状溶液，从而提高萃取效率并缩短平衡时间。在分析过程中包含冰-水浴萃取步骤时，观察到药物回收率略有增加。以这种方式，获得了 255 至 340 倍的富集因子。使用两种跃迁（SRM1 和 SRM2）在选择反应监测模式（SRM）下进行数据采集，允许同时对分析物进行鉴定和定量。此外，还进行了信息依赖采集（IDA）扫描，以对第二个跃迁不存在或强度较低的分析物进行鉴定，这也为其他分析物提供了额外的确认。优化后的 US-IL-DLLME-LC-QqLIT-MS 方法表现出良好的精密度水平，相对标准偏差值在 1.1%至 11.3%之间。检测限和定量限分别为 0.2-60ngL(-1)和 1.0-142ngL(-1)。在废水样品中对目标分析物的萃取中获得了良好的富集因子（255-340）和回收率（88-111%）。该方法已成功应用于分析位于阿尔梅里亚（西班牙）的城市污水处理厂的废水废水样品，结果表明废水中存在氟芬那酸和美托洛尔，浓度分别为 0.1 和 1.3μg L(-1)。
