Determination of Very Low Concentration of Bisphenol A in Toys and Baby Pacifiers Using Dispersive Liquid–Liquid Microextraction by In Situ Ionic Liquid Formation and High-Performance Liquid Chromatography

Abstract

Bisphenol A (BPA) is a chemical compound used in the manufacturing of plastics and resins whose presence in the body in low concentrations can cause serious health problems. Due to this, there is a growing interest in the scientific community to develop analytical methods that allow quantifying trace concentrations of BPA in different types of samples. The determination of this compound in toys made of plastics that can be manipulated by children leads to an extra concern, because it is possible for BPA to enter the body by introducing these toys into the mouth. This work presents a novel procedure to the quickly and easily quantification of trace levels of BPA in samples of toys and pacifiers according to the current demanding regulations. The determination of very low levels of BPA was carried out by ionic liquid dispersive liquid–liquid microextraction (IL-DLLME) followed by high-performance liquid chromatography (HPLC). The formation in situ of the ionic liquid (IL) 1-octyl-3-methylimidazolium bis((trifluoromethane)sulfonyl)imide ([C8MIm] [NTf2]), was achieved by mixing 1-octyl-3-methylimidazolium chloride ([C8MIm]Cl) and lithium bis(trifluoromethanesulfonyl)imide ([NTf2]Li) aqueous solutions, reaching an instant dispersion whose cloud of microdrops allows the total extraction of BPA in the IL from aqueous solutions. After centrifugation, BPA concentration in the sedimented phase was determined by HPLC. The optimal experimental conditions for the microextraction and determination of BPA in the IL were studied. The total extraction was achieved at pH 4, heating the sample at 30 °C for 5 min, using 100 µL of IL precursor volume, and spinning after the formation of dispersion at 3000 rpm for 10 min. The enrichment factor (EF) and detection limit (LOD) reached with the procedure were 299 and 0.19 µg L−1, respectively. The relative standard deviation for ten replications at the 0.5 µg L−1 level was 5.2%. Recovery studies showed a mean value for BPA recovery percentage in the samples of 99%. Additionally, a hybrid model was applied to characterize the extraction kinetics. This simple, low cost and fast method simplifies traditional microextraction techniques, representing an outstanding alternative.

Advances Brought by Hydrophilic Ionic Liquids in Fields Involving Pharmaceuticals

“…At this point, a hydrophobic IL capable of being dispersed through the sample is yielded, producing microdroplets where the target analytes are enriched [ 121 ]. Reports on the determination of antibiotics [ 152 ], phenolic endocrine-disrupting chemicals [ 153 , 154 ] and triazole fungicides [ 155 ] in a multitude of samples (viz., food, environmental water samples, toys, pacifiers, industrial effluents) with the aid of such an approach are available. Examples of ILs applied are mono- (e.g., [C n C 1 im]Cl/Br, [C n C 4 im]Br and [C 7 H 7 C 1 im]Cl) and dicationic (e.g., [C 4 (C n im) 2 ]Br 2 ) imidazolium-based, together with [PF 6 ] – and [NTf 2 ] – salts as the ion exchange agent [ 152 , 153 , 154 , 155 ].…”

“…Reports on the determination of antibiotics [ 152 ], phenolic endocrine-disrupting chemicals [ 153 , 154 ] and triazole fungicides [ 155 ] in a multitude of samples (viz., food, environmental water samples, toys, pacifiers, industrial effluents) with the aid of such an approach are available. Examples of ILs applied are mono- (e.g., [C n C 1 im]Cl/Br, [C n C 4 im]Br and [C 7 H 7 C 1 im]Cl) and dicationic (e.g., [C 4 (C n im) 2 ]Br 2 ) imidazolium-based, together with [PF 6 ] – and [NTf 2 ] – salts as the ion exchange agent [ 152 , 153 , 154 , 155 ]. A hydrophobic IL containing the imidazolium cation and the [PF 6 ] – or [NTf 2 ] – anions from the parent IL and the ion exchange salt, respectively, is yielded, easily dispersing through the sample with no need of an extra dispersant [ 152 , 153 , 154 , 155 ].…”

“…Examples of ILs applied are mono- (e.g., [C n C 1 im]Cl/Br, [C n C 4 im]Br and [C 7 H 7 C 1 im]Cl) and dicationic (e.g., [C 4 (C n im) 2 ]Br 2 ) imidazolium-based, together with [PF 6 ] – and [NTf 2 ] – salts as the ion exchange agent [ 152 , 153 , 154 , 155 ]. A hydrophobic IL containing the imidazolium cation and the [PF 6 ] – or [NTf 2 ] – anions from the parent IL and the ion exchange salt, respectively, is yielded, easily dispersing through the sample with no need of an extra dispersant [ 152 , 153 , 154 , 155 ]. As claimed with the extraction of tetracyclines from food samples [ 152 ], the analytical performance of in situ IL-DLLME using [C 7 H 7 C 1 im]Cl and NH 4 PF 6 (CFs = 25–98 and limits of detection = 0.12–0.45 µg/L) matched or even overwhelmed that of other previously reported methods including conventional IL-DLLME using hydrophobic ILs and SPE.…”

“…To sum up, applications of hydrophilic ILs in DLLME reveal a clear inclination to imidazolium-based ILs [ 148 , 149 , 150 , 151 , 152 , 153 , 154 , 155 , 156 ]. Thus, there is still room for further exploring other IL chemical structures, particularly as an attempt to overcome possible technical difficulties regarding practical execution and compatibility with the analytical equipment.…”

A fast, low-cost and eco-friendly method for routine determination of Bisphenol-A in landfill leachate employing vortex assisted liquid-liquid extraction

“…For that, a pre-concentration and/or clean-up step have been used to prepare the sample prior to extraction and analytical determination of BPA, allowing the quantification of BPA at trace levels in water and plastic materials as toys. [10,11]. In general, the sample preparation has been performed by methods based on liquid or solid phase extraction.…”