Abstract
Abstract We report a 3D-pen fabricated electrochemical sensor using biodegradable carbon black/polylactic acid (PLA) filament for on-site monitoring of lead and copper in aqueous and hydroethanolic media. The sensors consist of 3D-printed PLA concentric tubes filled with conductive carbon-black/PLA in a similar design to a disc working electrode. Under optimized square-wave anodic-stripping-voltammetry (SWASV) parameters, the proposed sensor presented wide linear ranges (R2 > 0.99) in aqueous (up to 870 μg L−1 for both metals) and hydroethanolic media (up to 200 μg L−1 for lead and up to 400 μg L−1 for copper). The limits of detection were estimated as 1 and 2 μg L−1 for lead and copper in both media (100 s deposition time), respectively, below the strict limits established by regulatory agencies for water and fuel ethanol, with high precision (inter-day and inter-electrode RSD lower than 2.8%). The presence of Fe3+, Cd2+, Zn2+ and Hg2+ did not interfere in the detection of both metals. Recovery values for the analysis of fortified samples (tap-water and ethanol) ranged from 83% to 107%. Importantly, the concomitant presence of copper improved the sensitivity to lead in aqueous medium probably by the formation of a copper film, which did not occur in hydroethanolic medium.
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