Summary: | This manuscript reports the use of nanoparticle-modified voltammetric sensors for the rapid and green determination of chemical oxygen demand in river waters and waters from agricultural waste. Four different variants of modified electrodes have been prepared: CuO nanoparticles electrogenerated over Cu and covered with Nafion film (CuO/Cu-Nf), and graphite–epoxy composites modified with Cu, CuO, and Cu–Ni alloy nanoparticles. The response features of these electrodes were assessed by calibrating them vs. glucose, glycine, ethyleneglycol, and hydrogenphtalate in alkaline media, as samples providing different difficulty in their (bio)degradation characteristics. The most sensitive electrode was demonstrated to be the (CuO/Cu-Nf) electrode, with an LOD of 12.3 mg O<sub>2</sub>·L<sup>−1</sup>. The joint information provided by the sensor array showed the ability of estimating both the organic load and the type of sample in terms of difficulty of degradation, in what can be named an intelligent sensor assembly.
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