title: Determination of eight fluoroquinolones in groundwater samples with ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction prior to high-performance liquid chromatography and fluorescence detection.
abstract: An ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4 mL of methanol), which increased the extraction efficiency and reduced the equilibrium time. For the DLLME procedure, the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)MIM] [PF(6)]) and methanol (MeOH) were used as extraction and disperser solvent, respectively. By comparing [C(8)MIM] [PF(6)] with 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM] [PF(6)]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)MIM] [PF(6)]) as extraction solvents, it was observed that when using [C(8)MIM] [PF(6)] the cloudy solution was formed more readily than when using [C(6)MIM] [PF(6)] or [C(4)MIM] [PF(6)]. 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 optimised. A slight increase in the recoveries of fluoroquinolones was observed when an ice-water bath extraction step was included in the analytical procedure (85-107%) compared to those obtained without this step (83-96%). Under the optimum conditions, linearity of the method was observed over the range 10-300 ng L(-1) with correlation coefficient >0.9981. The proposed method has been found to have excellent sensitivity with limit of detection between 0.8 and 13 ng L(-1) and precision with relative standard deviation values between 4.8 and 9.4% (RSD, n=5). Good enrichment factors (122-205) and recoveries (85-107%) were obtained for the extraction of the target analytes in groundwater samples. This simple and economic method has been successfully applied to analyse real groundwater samples with satisfactory results.
authors.affiliation: Department of Analytical Chemistry, University of Almería, La Cañada de San Urbano, 04120 Almería, Spain.
authors.forename: M M Parrilla
authors.initials: MM
authors.lastname: Vázquez
authors.forename: P Parrilla
authors.initials: PP
authors.lastname: Vázquez
authors.forename: M Martínez
authors.initials: MM
authors.lastname: Galera
authors.forename: M D Gil
authors.initials: MD
authors.lastname: García
mesh_terms: D005591:Chemical Fractionation; D002851:Chromatography, High Pressure Liquid / Q000191:economics; D004784:Environmental Monitoring / Q000379:methods*; D005453:Fluorescence; D024841:Fluoroquinolones / Q000032:analysis*; D060587:Groundwater / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry; D057230:Limit of Detection; D013997:Time Factors; D014465:Ultrasonics
chemical_list: D024841:Fluoroquinolones; D052578:Ionic Liquids