The presence and levels of the cyanobacterial toxins microcystin-LR, anatoxin-a, and cylindrospermopsin were measured in various Wisconsin waters where algal nuisance or bloom conditions were noted. Out of 74 samples analyzed, 36 had detectable levels of microcystin-LR (49%), and four had detectable levels of anatoxin-a (5%). Cylindrospermopsin, the toxin produced by Cylindrospermopsis (a warm water species that has been moving its range northward, including to Wisconsin), was not detected in the field samples tested. Concentrations of microcystin-LR ranged from 1.2 to 7600 microg L(-1). Anatoxin-a ranged from 0.68 to 1750 microg L(-1), which is the highest concentration reported from around the world. Cyanobacterial toxins, because of their high potency, deserve continued scrutiny by resource managers and public health officials responsible for recreational waters.
Beta-methylamino-L-alanine (BMAA) is a neurotoxic amino acid that can be produced by cyanobacteria in aqueous environments. To analyze this compound by gas chromatography/mass spectrometry (GC/MS), BMAA must be derivatized to a nonpolar, volatile compound. This can be accomplished by reacting BMAA with ethyl chloroformate. While carrying out electron ionization (EI) mass spectrometric analysis on the (13)C-labeled derivative, it was discovered that the formation of an ion with a peak at m/z 245.12 is the result of [CH(3)CH(2)O.] loss from the amino groups resulting from alpha-cleavage. This differs from previous reports that attributed this peak to alpha-cleavage of the carboxylic ester portion of the BMAA derivative. This finding is important for understanding BMAA derivative mass spectrometric fragmentation patterns and ultimately to properly identifying and quantifying BMAA. Fragmentation pathways for the formation of other major peaks observed in the EI mass spectra are also proposed.
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