VARIATION OF 2,3,4-TRIBROMOPYRROLE AND ITS SODIUM SULFAMATE SALT IN THE HEMICHORDATE SACCOGLOSSUS-KOWALEVSKII

We quantified spatial and temporal patterns of brominated pyrrole variation in the common marine hemichordate worm Saccoglossus kowalevskii. Using fast-atom bombardment mass spectrometry we found a novel sodium sulfamate salt (C4HBr3NO3SNa) of 2,3,4-tribromopyrrole (TBP)w that predominated over 2,3,4-TBP (11% vs 0.6% ash-free dry wt). There was no relationship between the total amounts of the 2 compounds. The sulfamate salt was concentrated in the hepatic region (50%), a possible site of synthesis or storage. 2,3,4-TBP was highest (1.5%) in the proboscis and tail, which are exposed to predation. No seasonal pattern was apparent for the sulfamate salt over a 30 mo sampling period. 2,3,4-TBP exhibited temporal increases, possibly associated with spawning. The sulfamate salt was not detectable by GC/MS techniques, raising the possibility that sulfonation may be more common than realized. The sulfamate salt may serve as the non-autotoxic stable precursor to the more volatile 2,3,4-TBP.