Analysis of Paraben Preservatives in Cosmetic Samples: Comparison of Three Different Dynamic Hollow Fiber Liquid-Phase Microextraction Methods

This study focused on a comparison of three different dynamic hollow fiber-based liquid-phase microextraction (DHF-LPME) methods for extraction and preconcentration of parabens from wastewater, toothpaste, cream, and shampoo samples. The first method is two-phase DHF-LPME, in which n-octanol was used as the extraction solvent. The second is three-phase DHF-LPME, in which n-octanol and basic aqueous solution were used as the extraction solvent and acceptor phase, respectively. High-performance liquid chromatography with UV detection (HPLC-UV) was applied for determination of the parabens in both methods. The third method is a recently introduced method; three-phase DHF-LPME based on two immiscible organic solvents (n-dodecane as organic solvent and acetonitrile as an acceptor phase). The quantitative analyses were performed by the use of gas chromatography-mass spectrometry (GC-MS) after injection port derivatization. The effect of different extraction conditions (i.e., extraction solvent, pH, ionic strength, stirring rate, and dynamic and extraction times) on the extraction efficiency of the parabens was investigated and optimized. All the three procedures provide similar working parameters characterized by high repeatability (3.9-6.3 %) and good linearity (correlation coefficient ranging from 0.989 to 0.998). Results of real sample analyses obtained by these three methods were highly correlated. Although all methods provide compatible alternatives for paraben analysis, the three-phase DHF-LPME based on two immiscible organic solvents may be a more appropriate technique due to its higher extraction efficiency and thus lower limits of detection (LODs). LODs for all the parabens ranged from 0.2 to 5.0 mu g L-1 using the two first methods combined with HPLC-UV. An improvement in sensitivity of several orders of magnitude was achieved using three-phase DHF-LPME based on two immiscible organic solvents followed by single-ion monitoring GC-MS analyses (0.01-0.2 mu g L-1) due to compatibility of this technique with GC instrument.