Graphene as a rational interface for enhanced adsorption of microcystin-LR from water.

Cyanotoxins such as microcystin-LR (MC-LR) represent a global environmental threat to ecosystems and drinking water supplies. The study investigated the direct use of graphene as a rational interface for removal of MC-LR via interactions with the aromatic ring of the ADDA1 chain of MC-LR and the sp2 hybridized carbon network of graphene. Intra-particle diffusion model fit indicated the high mesoporosity of graphene provided significant enhancements to both adsorption capacities and kinetics when benchmarked against microporous granular activated carbon (GAC). Graphene showed superior MC-LR adsorption capacity of 75.4 mg/g (Freundlich model) compared to 0.982 mg/g (Langmuir model) for GAC. Sorption kinetic studies showed graphene adsorbs 99% of MC-LR in 30 min, compared to zero removal for GAC after 24 hr using the same MC-LR concentration. Density functional theory (DFT), calculations showed that postulated π-based interactions align well with the NMR-based experimental work used to probe primary interactions between graphene and MC-LR adduct. This study proved that π-interactions between the aromatic ring on MC-LR and graphene sp2 orbitals are a dominant interaction. With rapid kinetics and adsorption capacities much higher than GAC, it is anticipated that graphene will offer a novel molecular approach for removal of toxins and emerging contaminants with aromatic systems.

Draft Genome Sequences of Bacteria with Cyanocidal Potential Isolated from Eutrophic Waters Associated with Cyanobacterial Harmful Algal Blooms.

Here, we report the draft genome sequences of nine bacterial species isolated from eutrophic waters associated with cyanobacterial harmful algal blooms with cyanocidal potential.

Remote sensing of the cyanobacteria life cycle: A mesocosm temporal assessment of a Microcystis sp. bloom using coincident unmanned aircraft system (UAS) hyperspectral imagery and ground sampling efforts.

Remote sensing technologies offer a consistent, spatiotemporal approach to assess water quality, which includes the detection, monitoring, and forecasting of cyanobacteria harmful algal blooms. In this study, a series of ex-situ mesoscale experiments were conducted to first develop and then monitor a Microcystis sp. bloom using a hyperspectral sensor mounted on an unmanned aircraft system (UAS) along with coincident ground sampling efforts including laboratory analyses and in-situ field probes. This approach allowed for the simultaneous evaluation of both bloom physiology (algal growth stages/life cycle) and data collection method on the performance of a suite of 41 spectrally-derived water quality algorithms across three water quality indicators (chlorophyll a, phycocyanin and turbidity) in a controlled environment. Results indicated a strong agreement between Lab and Field-based methods for all water quality indicators independent of growth phase, with regression R2-values above 0.73 for mean absolute percentage error (MAPE) and 0.87 for algorithm R2 values. Three of the 41 algorithms evaluated met predetermined performance criteria (MAPE and algorithm R2 values); however, in general, algal growth phase had a substantial impact on algorithm performance, especially those with blue and violet wave bands. This study highlights the importance of co-validating sensor technologies with appropriate ground monitoring methods to gain foundational knowledge before deploying new technologies in large-scale field efforts.

Graphene-Mediated removal of Microcystin-LR in chitosan/graphene composites for treatment of harmful algal blooms.

Water quality can be severely impacted by algal blooms alone, yet cyanotoxins, such as microcystin (MC), are potent underlying hazards produced by various species of cyanobacteria. Currently there is a need for environmentally compatible and economically viable media to address large scale application for HAB impacted waters. This study evaluated the interactions of chitosan/graphene (CSG) composites with three different species of cyanobacteria: Anabaena sp, Synechocystis sp, and Microcystis aeruginosa for both removal of algal optical density and toxins. Although results suggest that CSG has an algae dependent removal of density with a range of 40-90% removal, graphene/CSG is highly effective at MC toxin removal, removing >94% of MC-LR produced by Microcystis aeruginosa. Characterization by SEM and XRD revealed that 750 m2/g surface area graphene, imparts graphene morphology and functionality into the chitosan matrix surface, potentially enabling π-π interactions between graphene and the aromatic ring of microcystin. This proposed π-π removal mechanism of microcystin via the CSG chitosan biopolymer substrate offers a promising sustainable and selective media suitable for deployable treatment of HAB impacted waters.

Analytical Methods Incorporating Molecularly Imprinted Polymers (MIPs) for the Quantification of Microcystins: A Mini-Review.

Harmful algal blooms (HABs) negatively impact numerous natural waterways worldwide and have significant socioeconomic and health-related ramifications for local populations. In order to better detect, characterize, and mitigate bloom events, novel field deployable analytical technologies capable of quantifying common HAB toxins (e.g., microcystins) are of paramount importance. Toward this end, molecularly imprinted polymer (MIP) transducing elements used in conjunction with sensitive analytical techniques may be a useful tool for microcystin detection and quantification. Indeed, several efforts have been undertaken in the last decade (2010-2020) to combine the selectivity provided by MIPs with various analytical methods, many of which are adaptable for in-field analysis. This review presents a summary of the current state of microcystins detection methods incorporating MIPs with a focus on potentiometry, photoelectrochemistry, liquid chromatography, quartz crystal microbalance, competitive ELISA, interferometry, and immunochromatography. Furthermore, a perspective detailing trends and observations from the current body of literature is provided to guide future MIP-based microcystin and other HAB toxin detection efforts with a specific focus on deployable analytical platforms.