Determination of personal care products in water using UHPLC–MS after solid phase extraction with mesoporous silica‐based MCM‐41 functionalized with cyanopropyl groups

Abstract

A silica-based MCM-41 mesoporous material functionalized with cyanopropyl groups has been synthesized by cocondensation, characterized and applied to preconcentrate six parabens and three UV filters in river and swimming-pool waters. The analytes were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry, according to the Directive 96/23/EC. Even though matrix effect was negligible, quantification in river water samples with the standard addition approach improved the recoveries obtained using solvent-based and even with matrixmatched calibration. The method quantification limits in river water samples were 0.05 ng/mL for 2,4-dihydroxybenzophenone and 0.01 ng/mL for the rest. Recoveries, evaluated for a concentration level of 0.5 ng/L, were in the range 93.5-107.6% for parabens and in the range 64.2-85.8% for UV filters, with relative standard deviations intraday ≤10.2 and 10.8%, respectively. This parameter, evaluated for a concentration level of 0.1 ng/L, ranged between 98.3 and 110.4% for parabens and between 61.9 and 89.9% for UV filters, with relative standard deviation intraday ≤15.3 and 15.5%, respectively. The two UV filters with lower recoveries were the most affected by the addition of sodium chloride. River and swimming pool waters were analyzed and all the personal care products were found in the swimming pool water, whereas only methylparaben was detected in the river water. K E Y W O R D Sfunctionalized MCM-

The Application of Liquid Chromatography for the Analysis of Organic UV Filters in Environmental and Marine Biota Matrices

“…Most of the studies reported in this review used the SPE procedure, sometimes modified according to the chemical structure of the UVF to be determined [45,51,52,56,60,61,69,70]. Other authors developed alternative extraction techniques using a semipermeable membrane device for the simultaneous extraction of different UVF classes [49].…”

“…For the determination of organic UVFs in investigated matrices, chromatographic separation was generally performed on reverse phase C18 columns, except for two studies that used a C8 column [51,60].…”

“…The main goal in sample preparation is to design stationary phases for dealing with the retention of polar and apolar analytes simultaneously. An attempt to improve the selectivity or specificity toward target analytes was developed by Kharbouche et al using a solid phase extraction (SPE) with silica-based mesoporous, functionalized with cyanopropyl groups for the determination of BP-1, 4-HBP, and 4,4 ′ -DHBP in river and swimming pool water [51]. The quantification of these emerging contaminants in water was carried out using LC-MS/MS in both PI and negative ionization (NI) modes.…”

Benzophenones in the Environment: Occurrence, Fate and Sample Preparation in the Analysis

“…Despite the overall good characteristics, the method was time-consuming, given that 100-200 mL of sample was passed with a flow rate of 5 mL/min (20–40 min extraction time), plus 30 min of solvent evaporation was required [ 66 ]. Kharbouche et al proposed the use of mesoporous silica-based materials MCM-41 and MCM-41-CN(a cyanopropyl derivatized MCM-41) as SPE sorbents, for the extraction of four BPs [ 67 ]. They optimized the parameters of the method and found that the optimum pH for MCM-41 was 6.0 and for MCM-41-CN was 3.5.…”

“…The intra-day precisions of the method were between 6.0 and 15.5 (spiked with 0.1 ng/L BPs) and from 8.2 to 10.8 (spiked with 0.5 ng/L). This hints towards a rather irreproducible method [ 67 ]. Likewise, Sun et al proposed an extraction method using molecularly imprinted polymers as SPE sorbents, for the analysis of tap water and river water [ 68 ].…”