The neurotoxin β-N-methylamino-L-alanine (BMAA), suspected to trigger neurodegenerative diseases, can be produced during cyanobacterial bloom events and subsequently affect ecosystems and water sources. Some of its isomers including β-amino-N-methylalanine (BAMA), N-(2-aminoethyl) glycine (AEG), and 2,4-diaminobutyric acid (DAB) may show different toxicities than BMAA. Here, we set out to provide a fast and sensitive method for the monitoring of AEG, BAMA, DAB and BMAA in surface waters. A procedure based on aqueous derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was investigated for this purpose. Under optimized conditions, a small aqueous sample aliquot (5 mL) was spiked with BMAA-d3 internal standard, subjected to FMOC-Cl derivatization, centrifuged, and analyzed. The high-throughput instrumental method (10 min per sample) involved on-line pre-concentration and desalting coupled to ultra-high-performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS). Chromatographic gradient and mobile phases were adjusted to obtain suitable separation of the 4 isomers. The method limits of detection were in the range of 2–5 ng L-1. In-matrix validation parameters including linearity range, accuracy, precision, and matrix effects were assessed. The method was applied to surface water samples (n = 82) collected at a large spatial scale in lakes and rivers in Canada. DAB was found in >70% of samples at variable concentrations (<3–1,900 ng L-1), the highest concentrations corresponding to lake samples in cyanobacterial bloom periods. BMAA was only reported (110 ng L-1) at one HAB-impacted location. This is one of the first studies to report on the profiles of AEG, BAMA, DAB, and BMAA in background and impacted surface waters.
Duy, S. V., Munoz, G., Dinh, Q. T., Do, D. T., Simon, D. F., & Sauvé, S. (2019). Analysis of the neurotoxin β-N-methylamino-L-alanine (BMAA) and isomers in surface water by FMOC derivatization liquid chromatography high resolution mass spectrometry. PLoS ONE, 14(8). https://doi.org/10.1371/journal.pone.0220698