Electrochemical Determination of Oxyanions: Measurands, Signal Attribution, and the Limits of Analytical Translation

Electrochemical sensors for oxyanion detection are widely reported across environmental, industrial, and biological contexts, with recent literature often emphasising material innovation and increasingly low detection limits. Despite this activity, translation beyond laboratory demonstrations remains limited, raising questions about how electrochemical signals are interpreted and validated. In this review, recent electrochemical oxyanion sensors are examined from a measurement-centred perspective, focusing on how signals are generated, conditioned, and calibrated across major sensing strategies, including direct faradaic detection, modified-electrode and electrocatalytic systems, accumulation-based approaches, and enzyme- or mediator-assisted architectures. Rather than cataloguing sensor materials or device configurations, the analysis examines the assumptions underlying commonly reported performance metrics. Across sensing strategies, signal behaviour is frequently governed by interfacial chemistry, surface history, and experimental constraints rather than by invariant properties of the target oxyanion. Consequently, sensitivity, selectivity, and detection limits often reflect context-dependent behaviour within narrowly defined laboratory regimes. By synthesising these patterns, the review identifies recurring interpretive limitations in how electrochemical responses are linked to analyte determination. The resulting framework clarifies the analytical basis of the existing literature and highlights design-relevant constraints and validation practices that must be addressed for electrochemical oxyanion sensors to progress from feasibility demonstrations to robust analytical tools.