Highly sensitive and simultaneous electrochemical determinations of non-steroidal anti-inflammatory drugs in water using nanostructured carbon-based paste electrodes

Simple and fast simultaneous quantifications in water of anti-inflammatory drugs, which belong to the emerging pollutants, represents a great challenge for water quality control. The development of electrochemical methods to meet the simultaneous and concomitant detection requirements depends mainly on the electrode material. The fullerene-carbon nanofiber (FULL/CNF) and graphene-carbon nanotubes (GR/CNT) paste electrodes as sensing elements were employed for the first time for the determination of diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP) simultaneously and concomitantly. The comparative morphostructural and electrochemical characterizations of both electrodes were achieved by scanning electron microscopy (SEM) and cyclic voltammetry (CV). Differential-pulsed voltammetry (DPV), chronoamperometry (CA) and multiple-pulsed amperometry (MPA) were used for detection tests. FULL/CNE electrode was suitable to develop a simultaneous DPV-based detection methodology that allowed reaching the lowest limit of detections of 0.230 nM for DCF, 0.310 nM for NPX and 0.180 nM for IBP. GR/CNT electrode did not provide stability for DPV-based detection, but the lowest limits of detection of 0.149 nM for DCF, 0.809 nM for NPX and 0.640 nM for IBP were achieved by MPA-based methodology. Both electrodes, linked to specific detection technique, showed good reproducibility, stability and ability to measure DCF, NPX and IBP simultaneously in aqueous solution. The satisfactory results achieved by analysis of real surface water sample (Bega River, Tim isoara city, Romania) indicated that the proposed voltammetric and amperometric methodologies using both electrodes have great potential for practical applications in analysis of different water samples.