Cost-effective screen-printed carbon electrode biosensors for rapid detection of microcystin-LR in surface waters for early warning of harmful algal blooms.

Abstract

Microcystins (MCs) are toxins produced by cyanobacteria commonly found in harmful algal blooms (HABs). Due to their toxicity to humans and other organisms, the World Health Organization (WHO) sets a guideline of 1 μg L-1 for microcystin-leucine-arginine (MC-LR) in drinking water. However, current analytical techniques for the detection of MC-LR such as liquid chromatography-mass spectrometry (LC-MS) and ELISA are costly, bulky, time-consuming, and mostly conducted in a laboratory, requiring highly trained personnel. An analytical method that can be used in the field for rapid determination is essential. In this study, an anti-MC-LR/MC-LR/cysteamine-coated screen-printed carbon electrode (SPCE) biosensor was newly developed to detect MC-LR, bioelectrochemically, in water. The functionalization of the electrode surface was confirmed with surface characterization methods. The sensor performance was evaluated by electrochemical impedance spectroscopy (EIS), obtaining a linear working range of MC-LR concentrations between 0.1 and 100 μg L-1 with a limit of detection (LOD) of 0.69 ng L-1. Natural water samples experiencing HABs were collected and analyzed using the developed biosensor, demonstrating the excellent performance of the biosensor with a relative standard deviation (RSD) of 0.65%. The interference tests showed minimal error and RSD values against other common MCs and possible coexisting ions found in water. The biosensor showed acceptable functionality with a shelf life of up to 12 weeks. Overall, the anti-MC-LR/MC-LR/cysteamine/SPCE biosensors can be an innovative solution with characteristics that allow for in situ, low-cost, and easy-to-use capabilities which are essential for developing an overarching and integrated "smart" environmental management system.