Microcystins, BMAA and BMAA isomers in 100-year-old Antarctic cyanobacterial mats collected during Captain RF Scott's Discovery Expedition

Microcystins (MCN), -N-methylamino-L-alanine (BMAA) and anatoxin-a were investigated in Antarctic cyanobacterial mats collected from Ross Island and the McMurdo Ice Shelf, East Antarctica during Captain Scott's Discovery' National Antarctic Expedition (1901-1904). Ultra-performance liquid chromatography-photodiode array detection (UPLC-PDA) and tandem mass spectrometry (MS/MS) analysis were used to quantify the cyanotoxins in seven cyanobacterial mat samples. MCNs were identified in six of the mat samples at concentrations from 0.5 to 16.1 mu gg(-1) dry weight. BMAA was found in one sample (528 ngg(-1) dry weight, total BMAA), as well as two BMAA isomers, 2,4-diaminobutyric acid (DAB) and N-(2-aminoethyl) glycine (AEG) in six samples up to 6.56 and 6.79 gg(-1) dry weight, respectively. No anatoxin-a was detected. The findings confirm that MCNs, BMAA and BMAA isomers are preserved under dry herbarium conditions. The Discovery' cyanobacterial mat samples represent the oldest polar cyanobacterial samples found to contain cyanotoxins to date and provide new baseline data for cyanotoxins in Antarctic freshwater cyanobacterial mats from prior to human activity in Antarctica, the development of the ozone hole and current levels of climatic change.