Simultaneous voltammetric detection of cadmium(II), arsenic(III), and selenium(IV) using gold nanostar-modified...

The present work reports a newly developed square wave anodic stripping voltammetry (SWASV) methodology using novel gold nanostar-modified screen-printed carbon electrodes (AuNS/SPCE) and modified Britton-Robinson buffer (mBRB) for simultaneous detection of trace cadmium(II), arsenic(III), and selenium(IV). During individual and simultaneous detection, Cd²⁺, As³⁺, and Se⁴⁺ exhibited well-separated SWASV peaks at approximately - 0.48, - 0.09, and 0.65 V, respectively (versus Ag/AgCl reference electrode), which enabled a highly selective detection of the three analytes. Electrochemical impedance spectrum tests showed a significant decrease in charge transfer resistance with the AuNS/SPCE (0.8 kΩ) compared with bare SPCE (2.4 kΩ). Cyclic voltammetry experiments showed a significant increase in electroactive surface area with electrode modification. The low charge transfer resistance and high electroactive surface area contributed to the high sensitivity for Cd²⁺ (0.0767 μA (0.225 μg L^-1)^-1), As³⁺ (0.2213 μA (μg L^-1)^-1), and Se⁴⁺ (μA (μg L^-1)^-1). The three analytes had linear stripping responses over the concentration range of 0 to 100 μg L^-1, with the obtained LoD for Cd²⁺, As³⁺, and Se⁴⁺ of 1.6, 0.8, and 1.6 μg L^-1, respectively. In comparison with individual detection, the simultaneous detection of As³⁺ and Se⁴⁺ showed peak height reductions of 40.8% and 42.7%, respectively. This result was associated with the possible formation of electrochemically inactive arsenic triselenide (As₂Se₃) during the preconcentration step. Surface water analysis resulted in average percent recoveries of 109% for Cd²⁺, 93% for As³⁺, and 92% for Se⁴⁺, indicating the proposed method is accurate and reliable for the simultaneous detection of Cd²⁺, As³⁺, and Se⁴⁺ in real water samples. Graphical abstract.