Utilization of an ionic liquid in situ preconcentration method for the determination of the 15 + 1 European Union polycyclic aromatic hydrocarbons in drinking water and fruit-tea infusions.

An ionic liquid (IL) in situ preconcentration method was optimized and applied to the monitoring of the 15 + 1 European Union polycyclic aromatic hydrocarbons in water and fruit-tea infusions. The optimized method utilizes 10 mL of water (or infusion) containing 38 µL of the IL 1-butyl-3-methylimidazolium chloride and a content of 36.1 g/L NaCl, which are mixed with Li-NTf2 (340 µL, 0.2 g/mL), followed by vortex (4 min) and centrifugation (5 min). The obtained microdroplet containing hydrocarbons is diluted with acetonitrile and injected into an HPLC with UV/Vis and fluorescence detection. The method presented average enrichment factors of 127 for water (tap water and bottled water) and 27 for two fruit-tea infusions; with average relative recoveries of 86.7 and 106% for water and fruit-tea infusions, respectively. The method was sensitive, with detection limits ranging from 0.001 to 0.050 ng/mL in water, and from 0.010 to 0.600 ng/mL in fruit-tea infusions, for the fluorescent hydrocarbons. Real extraction efficiencies ranged from 12.7 to 58.7% for water, and from 20.2 to 117% for the infusions. The method was also fast (~12 min) and free of organic solvents in the extraction step.

A novel in situ preconcentration method with ionic liquid-based surfactants resulting in enhanced sensitivity for the extraction of polycyclic aromatic hydrocarbons from toasted cereals.

A preconcentration procedure utilizing IL-based surfactants it is described for the first time. The procedure is based on transforming a water-soluble IL-based surfactant, 1-hexadecyl-3-butylimidazolium bromide (C16C4Im-Br), into a water-insoluble IL, 1-hexadecyl-3-butylimidazolium bis[(trifluoromethane)sulfonyl]imide (C16C4Im-NTf2), via a simple metathesis reaction. The preconcentration procedure is used in combination with a micellar microwave-assisted extraction (MMAE) method for the analysis of sixteen polycyclic aromatic hydrocarbons (PAHs) from toasted cereals. The obtained microdroplet of C16C4Im-NTf2 containing the extracted PAHs is then diluted with acetonitrile and injected into a high-performance liquid chromatograph (HPLC) employing UV-vis and fluorescence detection. This in situ preconcentration step highly improves the sensitivity of the MMAE despite the complexity of the solid matrix. The developed in situ preconcentration method exhibited almost quantitative extraction efficiencies (80-95% in average) for the PAHs studied, and good precision values (lower than 14%). The overall MMAE+in situ preconcentration method presented limits of detection down to 0.03 µg kg⁻¹.

Use of ionic liquid aggregates of 1-hexadecyl-3-butyl imidazolium bromide in a focused-microwave assisted extraction method followed by high-performance liquid chromatography with ultraviolet and fluorescence detection to determine the 15+1 EU priority PAHs in toasted cereals ("gofios").

A focused-microwave assisted extraction method using aggregates of the ionic liquid (IL) 1-hexadecyl-3-butylimidazolium bromide (HDBIm-Br) followed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection and single-channel fluorescence detection (FLD) has been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in toasted cereals ("gofios") of different nature (wheat, barley, rye, and maize corn) from the Canary Islands, Spain. The optimized HPLC-UV-vis/single-channel FLD method takes 40 min for the chromatographic run with limits of detection varying between 0.02 and 4.01 ng mL(-1) for the fluorescent PAHs from the European Union (EU) priority list in foods, and 20.5 ng mL(-1) for the non-fluorescent PAH cyclopenta[c,d]pyrene (CPP). The optimized microwave step presented extractions recoveries ranging from 70.1 to 109% and precision values lower than 12.6% (as relative standard deviation), using an extraction time of 14 min. The extraction method also utilizes low amounts of sample (0.1g), and low amounts of IL (77 mg), avoiding completely the use of organic solvents.

Dispersive liquid-liquid microextraction versus single-drop microextraction for the determination of several endocrine-disrupting phenols from seawaters.

Two liquid-phase microextraction procedures: single-drop microextraction (SDME) and dispersive liquid-liquid microextraction (DLLME), have been developed for the determination of several endocrine-disrupting phenols (EDPs) in seawaters, in combination with high-performance liquid chromatography (HPLC) with UV detection. The EDPs studied were bisphenol-A, 4-cumylphenol, 4-tertbutylphenol, 4-octylphenol and 4-n-nonylphenol. The optimized SDME method used 2.5 microL of decanol suspended at the tip of a micro-syringe immersed in 5 mL of seawater sample, and 60 min for the extraction time. The performance of the SDME is characterized for average relative recoveries of 102+/-11%, precision values (RSD)<9.4% (spiked level of 50 ng mL(-1)), and detection limits between 4 and 9 ng mL(-1). The optimized DLLME method used 150 microL of a mixture acetonitrile:decanol (ratio 15.7, v/v), which is quickly added to 5 mL of seawater sample, then subjected to vortex during 4 min and centrifuged at 2000 rpm for another 5 min. The performance of the DLLME is characterized for average relative recoveries of 98.7+/-3.7%, precision values (RSD)<7.2% (spiked level of 20 ng mL(-1)), and detection limits between 0.2 and 1.6 ng mL(-1). The efficiencies of both methods have also been compared with spiked real seawater samples. The DLLME method has shown to be a more efficient approach for the determination of EDPs in seawater matrices, presenting enrichment factors ranging from 123 to 275, average relative recoveries of 110+/-11%, and precision values (RSD)<14%, when using a real seawaters (spiked level of 3.5 ng mL(-1)).