title: Comparison of two ionic liquid dispersive liquid-liquid microextraction approaches for the determination of benzoylurea insecticides in wastewater using liquid chromatography-quadrupole-linear ion trap-mass spectrometry: evaluation of green parameters.
abstract: Two dispersive liquid-liquid microextraction (DLLME) approaches including temperature-controlled ionic liquid dispersive liquid-liquid microextraction (TCIL-DLLME) and ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) were compared for the extraction of six benzoylurea insecticides (diflubenzuron, triflumuron, hexaflumuron, teflubenzuron, lufenuron and flufenoxuron) from wastewater samples prior to their determination by high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS/MS). Influential parameters affecting extraction efficiency were systematically studied and optimized and the most significant green parameters were quantified and compared. The best results were obtained using the US-IL-DLLME procedure, which employed the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and methanol (MeOH) as extraction and disperser solvent, respectively. US-IL-DLLME procedure was fast, easy, low environmental toxicity and, it was also able to successfully extract all selected benzoylureas. This method was extensively validated with satisfactory results: limits of detection and quantification were in the range 0.5-1.0 ng L(-1) and 1.5-3.5 ng L(-1), respectively, whereas recovery rates ranged from 89 to 103% and the relative standard deviations were lower than 13.4%. The applicability of the method was assessed with the analysis of effluent wastewater samples from a wastewater treatment plant located in an agricultural zone of Almería (Spain) and the results indicated the presence of teflubenzuron at mean concentration levels of 11.3 ng L(-1). US-IL-DLLME sample treatment in combination with LC-QqLIT-MS/MS has demonstrated to be a sensitive, selective and efficient method to determine benzoylurea insecticides in wastewaters at ultra-trace levels.
authors.affiliation: Department of Chemistry and Physics, University of Almería, Centro de Investigación en Biotecnología Agroalimentaria, Area of Analytical Chemistry, BITAL, Campus de Excelencia Agroalimentario, ceiA3, La Cañada de San Urbano, E-04120 Almería, Spain.
authors.forename: M M Parrilla
authors.initials: MM
authors.lastname: Vázquez
authors.affiliation: Department of Chemistry and Physics, University of Almería, Centro de Investigación en Biotecnología Agroalimentaria, Area of Analytical Chemistry, BITAL, Campus de Excelencia Agroalimentario, ceiA3, La Cañada de San Urbano, E-04120 Almería, Spain.
authors.forename: P Parrilla
authors.initials: PP
authors.lastname: Vázquez
authors.affiliation: Department of Chemistry and Physics, University of Almería, Centro de Investigación en Biotecnología Agroalimentaria, Area of Analytical Chemistry, BITAL, Campus de Excelencia Agroalimentario, ceiA3, La Cañada de San Urbano, E-04120 Almería, Spain. Electronic address: mmartine@ual.es.
authors.forename: M Martínez
authors.initials: MM
authors.lastname: Galera
authors.affiliation: Department of Chemistry and Physics, University of Almería, Centro de Investigación en Biotecnología Agroalimentaria, Area of Analytical Chemistry, BITAL, Campus de Excelencia Agroalimentario, ceiA3, La Cañada de San Urbano, E-04120 Almería, Spain.
authors.forename: A Uclés
authors.initials: AU
authors.lastname: Moreno
mesh_terms: D001549:Benzamides / Q000032:analysis / Q000302:isolation & purification; D002851:Chromatography, High Pressure Liquid / Q000592:standards; D004132:Diflubenzuron / Q000032:analysis / Q000302:isolation & purification; D055772:Green Chemistry Technology / Q000592:standards*; D007093:Imidazoles / Q000737:chemistry*; D007306:Insecticides / Q000032:analysis / Q000302:isolation & purification*; D052578:Ionic Liquids / Q000737:chemistry*; D059627:Liquid Phase Microextraction / Q000592:standards; D000432:Methanol / Q000737:chemistry; D010671:Phenylurea Compounds / Q000032:analysis / Q000302:isolation & purification; D012015:Reference Standards; D012997:Solvents / Q000737:chemistry; D053719:Tandem Mass Spectrometry / Q000592:standards*; D062065:Wastewater / Q000032:analysis*; D005466:Fluorocarbons
chemical_list: D001549:Benzamides; D004132:Diflubenzuron; D007093:Imidazoles; D007306:Insecticides; D052578:Ionic Liquids; D000432:Methanol; D010671:Phenylurea Compounds; D012997:Solvents; D062065:Wastewater; C446740:1-octyl-3-methylimidazolium hexafluorophosphate; C070364:fluphenacur; D005466:Fluorocarbons; C023957:triflumuron; C058039:hexafluoron; C052595:teflubenzuron; C067660:flufenoxuron
keywords: Dispersive liquid–liquid microextraction; Insecticides; Ionic liquid; Liquid chromatography–quadrupole-linear ion trap; Tandem mass spectrometry; Wastewater