Arseno-sugars from brown kelp (Ecklonia radiata) as intermediates in cycling of arsenic in a marine ecosystem

Abstract

The high concentration (relative to seawater) of arsenic in many marine animals eaten as human food has stimulated interest in the cycling of arsenic in the marine environment1. Although arsenic is present as arsenobetaine [(CH3)3As+CH2COO−] in the western rock lobster2 (Panulirus cygnus), the dusky shark3 (Carcharhinus obscurus) and the school whiting4 (Sillago bassensis) it is not clear what intermediate stages are involved in the biosynthesis of this compound from arsenate, the major form of arsenic in seawater5. We now report the isolation of the two main arsenical constituents of the brown kelp, Ecklonia radiata, and their identification as a 2-hydroxy-3-sulphopropyl-5-deoxy-5-(dimethylarsenoso)furanoside and a 2,3-dihy-droxypropyl-5-deoxy-5-(dimethylarsenoso)furanoside. A β-ribo structure for the sugar system is strongly indicated in each case (A and B below). Ecklonia is the major organism that concentrates arsenic in the coastal ecosystem to which the western rock lobster and school whiting belong. It is clear that the compounds described here could readily be further metabolized to arsenobetaine and may well be the source of arsenobetaine in marine fauna associated with the region.