Strategies for assessing the limit of detection in voltammetric methods: comparison and evaluation of approaches

The realm of analytical chemistry continues to struggle with defining and evaluating the limit of detection in analytical methods in the sense that a multitude of definitions, criteria, caveats, and methods have been proposed, developed, and adopted across disciplines. The last decade has seen a surge in the growth of electrochemical methods and studies in the field of forensic science and forensic chemistry. While many disciplines within forensic science have established method validation guidelines, the historical and current lack of electrochemical methods within forensic laboratories throughout the United States has left a major gap in knowledge, inhibiting the adoption and utilization of electrochemistry, which may serve as a powerful tool in many subdisciplines of forensics. As such, this work begins this discussion by focusing first on the limit of detection (LOD), with application toward both qualitative and quantitative methods. Both inorganic (ferrocyanide and lead) and organic (diphenylamine, naltrexone, and acetaminophen) target analytes were analyzed via two common voltammetry methods: cyclic voltammetry and square-wave voltammetry. The LOD for each analyte was estimated and/or calculated following a variety of literature-described methods and compared. The accuracy and reliability of these LOD characteristics based on the experimental data is described herein along with suggestions and recommendations. This manuscript is intended to compare the resulting LOD values from various methods and provide a starting point for the incorporation of electrochemistry into the forensic science laboratory, beginning a focused discussion on the development of validation guidelines and parameters needed for the adoption of this technology in forensic laboratories in order to meet the standards required by the criminal justice system.