Ultrasound-assisted dispersive liquid–liquid microextraction plus simultaneous silylation for rapid determination of salicylate and benzophenone-type ultraviolet filters in aqueous samples

• UA-DLLME plus simultaneous silylation to analyze hydroxylated UV filters in water.
• Ultrasound accelerated the mass transfer of DLLME and increased silylation reaction.
• The method provides good precision and detection limits at the ng/L level.
• The method is low cost and eco-friendly, and avoids carryover problems

A rapid procedure, using minimal amounts of solvent, for the reliable determination of five salicylate and benzophenone-type ultraviolet (UV) filters: ethylhexyl salicylate (EHS), 3,3,5-trimethyl-cyclohexyl salicylate (HMS), 2-hydroxy-4-methoxybenzophenone (BP-3), 2,4-dihydroxy-benzophenone (BP-1) and 2,2′-dihydroxy-4-methoxybenzophenone (BP-8), in aqueous samples is described. The method involves an ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) plus simultaneous silylation prior to their determination by gas chromatography–mass spectrometry (GC–MS). The parameters affecting the extraction and derivatization efficiency of the target UV filters from aqueous samples were systematically investigated and the conditions optimized. The optimal silylation and extraction conditions involved the rapid injection of a mixture of 750 μL of acetone (as a dispersant), 15 μL of tetrachloroethylene (as an extractant), and 20 μL of BSTFA (as a derivatizing agent) into a 10-mL volume of aqueous samples (pH 7.0) containing 0.5 g of sodium chloride in a glass tube with a conical bottom. After ultrasonication for 2.0 min and centrifugation at 5000 rpm (10 min), the sedimented phase 5.0 μL was directly introduced into the GC–MS. The limits of quantitation (LOQs) were less than 6 ng/L. The precision for these analytes, as indicated by the relative standard deviations (RSDs), was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 and 92%. The method was then applied to environmental aqueous samples, using a standard addition method, showing the occurrence of BP-3 in samples of both river water and municipal wastewater treatment plant (MWTP) effluents.