Growth of the harmful benthic cyanobacterium Microseira wollei is driven by legacy sedimentary phosphorous.

Models for cyanobacterial harmful algae blooms (cHABs) in fresh waters are usually predicated on the relationship between cyanobacterial ecology and dissolved nutrients, particularly phosphorous. Here we show legacy sediment-associated phosphorous as the primary driver of a benthic cHAB, not phosphorous in the water column. Biogeographical surveys by teams of citizen science volunteers working with the University of South Carolina identified over 200 distinct mats of Microseira wollei in Lake Wateree, SC based on toxin characterization. In sum these were estimated to affect approximately 175 km of the lake's shoreline. This growth occurred under water quality conditions that were near or below the regulatory total maximum daily load for phosphorous and nitrogen. A series of established predictive models for cyanobacterial biomass growth were applied retroactively to match the measured growth with measured water quality parameters. The only component of the system that successfully predicted microbial biomass was sedimentary phosphorous. Concentrations of the Lyngbya wollei toxins (LWTs) 1, 4, 5, and 6 were determined at multiple sites over an 18-month period and a toxin inventory for the lake was calculated. Toxin profiles between sites differed at the 95% level of confidence, establishing each site as a unique mat. An empirical model of toxin production potential based on sedimentary phosphorous was developed.

Emerging Lyngbya wollei toxins: A new high resolution mass spectrometry method to elucidate a potential environmental threat.

Mass spectrometric methods for the quantitative and qualitative analyses of algal biotoxins are often complicated by co-eluting compounds that present analytically as interferences. This issue is particularly critical for organic polyamines, where co-eluting materials can suppress the formation of cations during electrospray ionization. Here we present an extraction procedure designed specifically to overcome matrix-derived ion suppression of algal toxins in samples of Lyngbya wollei, a filamentous benthic algae known to produce several saxitoxin analogues. Lyngbya wollei samples were collected from a large, persistent harmful algal bloom in Lake Wateree, SC. Six known Lyngbya wollei-specific toxins (LWT1-6) were successfully resolved and quantified against saxitoxin using hydrophilic interaction liquid chromatography coupled with triple quadrupole and quadrupole time-of-flight mass spectrometry. The parent ions [M2+ - H+]+ were observed for LWTs 1-6 and the [M]2+ ion was observed for LWT5. High resolution mass spectra and unique fragmentation ions were obtained for LWTs 1-6. A dilution factor of 50 resulted in a linear calibration of saxitoxin in the algae matrix. Ion suppression was resolved by sample dilution, which led to linear, positive correlations between peak area and mass of the extracted sample (R2 > 0.96). Optimized sample extraction method and instrument parameters are presented.