Ultra-preconcentration and determination of selected pharmaceutical and personal care products in different water matrices by solid-phase extraction combined with dispersive liquid–liquid microextraction prior to ultra high pressure liquid chromatography

• Rapid and highly sensitive analysis of PPCPs in environmental water matrices at ppt levels.
• Method's advantages are high EF, very low MDLs and MQLs.
• Good analytical performance in different environmental water matrices.
• Suitable multiresidue method for the for environmental PPCPs occurrence studies.

Pharmaceutical and personal care products (PPCPs) are one of the most important classes of emerging contaminants. The potential of ecological and environmental impacts associated with PPCPs are of particular concern because they continually penetrate the aquatic environment. This work describes a novel ultra-preconcentration technique for the rapid and highly sensitive analysis of selected PPCPs in environmental water matrices at ppt levels. Selected PPCPs were rapidly extracted and concentrated from large volumes of aqueous solutions (500 and 250 mL) by solid-phase extraction combined with dispersive liquid–liquid microextraction (SPE–DLLME) and then analyzed using UHPLC–MS/MS. Experimental parameters were carefully investigated and optimized to achieve the best SPE–DLLME efficiency and higher enrichment factors. The best results were obtained using the ternary mixture acetonitrile/methanol/dichloromethane 3:3:4, v/v/v, both as SPE eluent and DLLME extractant/dispersive mixture. DLLME aqueous solution (5% NaCl, 10 mg L−1 TBAB) was also modified to improve the extraction efficiency of more hydrophilic PPCPs. Under the optimal conditions, an exhaustive extraction for most of the investigated analytes (recoveries >70%), with a precision (RSD <10%) and very high enrichment factors were attained for different aqueous matrices (drinking, sea, river and wastewater). Method detection and quantification limits were at very low ppt levels and below 1 and 3 ng L−1, respectively, for 15 of selected PPCPs. The proposed analytical procedure offers numerous advantages such as the simplicity of operation, rapidity, a high enrichment factor and sensitivity. So it is suitable for monitoring and studies of occurrence of PPCPs in different environmental compartments.