Magnetic dispersive solid-phase extraction using ZSM-5 zeolite/Fe₂O₃ composite coupled with screen-printed electrodes...

A novel, simple, fast, sensitive and environmentally friendly approach is presented to determine cadmium in urine samples, combining magnetic dispersive solid-phase extraction (MDSPE) for sample preparation and screen-printed carbon electrodes (SPCEs) for square-wave anodic stripping voltammetry. This association involves the miniaturization of sample preparation and measurement process. Firstly, cadmium was extracted directly from urine samples employing a ZSM-5/Fe₂O₃, then, the composite enriched with cadmium was deposited onto the SPCE and finally covered with a suitable electrolyte for electrochemical detection. Thereby, the elution and detection of cadmium were carried out in a single step. To optimize experimental parameters affecting MDSPE, a two-step multivariate strategy has been employed. The method has been evaluated under optimized extraction/elution conditions (i.e., type of sorbent, ZSM-5/Fe₂O_3; amount of sorbent, 10 mg; sample pH, 6.8; extraction time, 5.5 min; and HCl concentration, 0.5 M) using standard addition calibration. Standard addition calibration curves gave a good linearity in the range from 0 to 30 μg L^-1 with correlation coefficients ranging from 0.997 to 0.998 (N = 7). The limit of detection, evaluated empirically and statistically, ranged from 0.5 to 1.0 μg L^-1 and from 0.4 to 0.8 μg L^-1, respectively, which are lower than the threshold level established by the Ministry of Labour and Social Affairs (Spain) and World Health Organization for normal cadmium content in urine (i.e., 3.4 and 4.0 μg L^-1, respectively). The repeatability of the proposed method was evaluated at 5 and 20 μg L^-1 spiking levels obtaining coefficients of variation ranged between 12 and 15% (n = 6). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 92% and 1.3 μg L^-1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was applied to spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 89 to 98% and CV values ranged from 7% to 14%). Therefore, this is a new and successful contribution to the portable total analytical systems.