Enhanced detection of the algal toxin PbTx-2 in marine waters by atmospheric pressure chemical ionization mass spectrometry.

Rationale: Karenia brevis, a marine dinoflagellate, biosynthesizes a unique class of polyether toxins called brevetoxins that produce significant health, environmental and economic impacts in and along coastal waters. Previous application of liquid chromatography/mass spectrometry for detection of the most common brevetoxin, PbTx-2, has relied almost exclusively upon electrospray ionization (ESI). A different ionization source is proposed in this study with improved sensitivity ultimately leading to lower limit of detection compared to (+) ESI.

Methods: Brevetoxin standards and samples (PbTx-2) were analyzed by liquid chromatography/mass spectrometry using both (+) atmospheric pressure chemical ionization and (+) electrospray ionization sources.

Results: LC/MS with (+) APCI exhibited an order of magnitude improvement in the limit of detection (7.7 × 10(-4) pg mass on-column) compared to the same method using (+) ESI (7.5 × 10(-3) pg mass on-column). The calibration sensitivity of (+) APCI (1.3 × 10(3)) was also five times higher than positive mode (+) ESI (0.26 × 10(3)).

Conclusions: Positive mode APCI represents a significant improvement in detection and quantification of PbTx-2 by LC/MS allowing for smaller sample sizes compared to previous studies using (+) ESI. This in turn leads to higher throughput of samples during and after bloom events giving stakeholders detailed information on the fate of this potent marine toxin.