Evidence of the Presence of Dimethylated, Trimethylated and "Refractory' Arsenic Compounds in Estuarine Salt‐marsh Halophytes

Five species of halophytes were sampled in the salt marshes of the Tagus estuary, dried, ground and digested. They were further extracted with ethanol and the extracts passed through weak and strong cationic ion-exchange resins, purified through TLC and submitted to pyrolysis mass spectrometry and HPLC–ICP/MS. Arsenic content and hydride-forming arsenic species were verified, in each step, by GF–AA and HG–QFAA. A high content of arsenic was found in the samples of halophytes studied, both di- and tri-methylated arsenic compounds being present. A considerable fraction of this arsenic content seems to be refractory to hydride generation. Moreover, the arsenic fraction found seems to have the same ion-exchange behaviour as the refractory fractions formerly studied in estuarine water. A partial characterization of these structures by pyrolysis–GC–MS suggests the presence of arsenobetaine and arsenocholine compounds. Furthermore, HPLC–ICP/MS data seem to confirm the presence of these compounds. In addition, the latter hyphenated technique strongly suggests the presence of a number of other organoarsenicals including tetramethylarsonium (TMAs), trimethylarsine oxide (TMAO), cacodylate (DMA) and possibly an arsenosugar-type compound. © 1997 by John Wiley & Sons, Ltd.