Cyanobacteria harmful algal blooms are increasing in frequency and cyanotoxins have become an environmental and public concern in the U.S. and worldwide. In this Review, the majority of reported studies and developments of electrochemical affinity biosensors for cyanotoxins are critically reviewed and discussed. Essential background information about cyanobacterial toxins and electrochemical biosensors is combined with the rapidly moving development of electrochemical biosensors for these toxins. Current issues and future challenges for the development of useful electrochemical biosensors for cyanotoxin detection that meet the demands for applications in field freshwater samples are discussed. The major aspects of the entire review article in a prescribed sequence include (i) the state-of-the-art knowledge of the toxicity of cyanotoxins, (ii) important harmful algal bloom events, (iii) advisories, guidelines, and regulations, (iv) conventional analytical methods for determination of cyanotoxins, (v) electrochemical transduction, (vi) recognition receptors, (vii) reported electrochemical biosensors for cyanotoxins, (viii) summary of analytical performance, and (ix) recent advances and future trends. Discussion includes electrochemical techniques and devices, biomolecules with high affinity, numerous array designs, various detection approaches, and research strategies in tailoring the properties of the transducer-biomolecule interface. Scientific and engineering aspects are presented in depth. This review aims to serve as a valuable source to scientists and engineers entering the interdisciplinary field of electrochemical biosensors for detection of cyanotoxins in freshwaters.

Microcystin-LR (MC-LR), an algal toxin (cyanotoxin) common in sources of drinking water, poses a major human health hazard due to its high toxicity. In this study, UV/chlorine was evaluated as a potentially practical and effective process for the degradation of MC-LR. Via mass spectrometry analysis, fewer chlorinated-MC-LR products were detected with UV/chlorine treatment than with chlorination, and a transformation pathway for MC-LR by UV/chlorine was proposed. Different degrees of rapid degradation of MC-LR were observed with varying pH (6-10.4), oxidant dosage (0.5-3 mg L), natural organic matter (0-7 mg L), and natural water sources. In contrast to the formation of primarily chloroform and dichloroacetic acid in deionized water where MC-LR serves as the only carbon source, additional chlorinated disinfection byproducts were produced when sand filtered natural water was used as a background matrix. The UV/chlorine treated samples also showed quantitatively less cytotoxicity in vitro in HepaRG human liver cell line tests than chlorination treated samples. Following 16 min (96 mJ cm) of UV irradiation combined with 1.5 mg L chlorine treatment, the cell viability of the samples increased from 80% after exposure to 1 mg L MC-LR to 90%, while chlorination treatment evidenced no reduction in cytotoxicity with the same reaction time.

Electrochemical impedance spectroscopy (EIS), an extremely sensitive analytical technique, is a widely used signal transduction method for the electrochemical detection of target analytes in a broad range of applications. The use of nucleic acids (aptamers) for sequence-specific or molecular detection in electrochemical biosensor development has been extensive, and the field continues to grow. Although nucleic acid-based sensors using EIS offer exceptional sensitivity, signal fidelity is often linked to the physical and chemical properties of the electrode–solution interface. Little emphasis has been placed on the stability of nucleic acid self-assembled monolayers (SAMs) over repeated voltammetric and impedimetric analyses. We have studied the stability and performance of electrochemical biosensors with mixed SAMs of varying length thiolated nucleic acids and short mercapto alcohols on gold surfaces under repeated electrochemical interrogation. This systematic study demonstrates that signal fidelity is linked to the stability of the SAM layer and nucleic acid structure and the packing density of the nucleic acid on the surface. A decrease in packing density and structural changes of nucleic acids significantly influence the signal change observed with EIS after routine voltammetric analysis. The goal of this article is to improve our understanding of the effect of multiple factors on EIS signal response and to optimize the experimental conditions for development of sensitive and reproducible sensors. Our data demonstrate a need for rigorous control experiments to ensure that the measured change in impedance is unequivocally a result of a specific interaction between the target analyte and nucleic recognition element.

The collection, storage, and reuse of rainwater collected in rain barrels from urban rooftop areas assists municipalities in achieving stormwater management objectives and in some areas also serves as an adjunct resource for domestic water supplies. In this study, rainwater reuse and levels of select microbial indicators were monitored for six residential rain barrels located in the Shepherd Creek watershed of Cincinnati, Ohio. Water from rain barrels typically had poor microbial quality and was used for watering indoor and outdoor plants. Rain barrel water chemistry was slightly acidic, exhibited wide ranges in conductivity, turbidity, and total organic carbon (TOC) concentrations and gave no evidence of the presence of cyanobacterial microcystin toxins. Selected microbial water-quality indicators indicated that counts of total coliform and enterococci were consistently above U.S. Environmental Protection Agency standards for secondary recreational contact water-quality standards. Residential rain barrels can provide water appropriate for low-contact reuses (such as plant watering), although there may be transient periods of high levels of indicator bacteria in the collected water.(KEY TERMS: stormwater management; stormwater retrofits; green infrastructure; rain barrels; watershed management; microbial water quality.)