For 30 yr, a persistent foam cover has been observed during the summer months in the Rhine River beneath the Rhine Fall, a waterfall near Schaffhausen, Switzerland. This phenomenon has been a matter of public concern ever since its first appearance, but all previous attempts to clarify the origin of this foam had remained inconclusive. With the aid of electrospray LC-MS, triterpene saponins and mono- and digalactosyldiacylglycerolipids (MGDAG and DGDAG), two classes of tensioactive metabolites occurring in the aquatic plant Ranunculus fluitans Lamk. (Ranunculaceae), were detected in river water and foam samples. Saponin concentrations in water and foam samples were monitored at regular intervals during the years 1998 and 2000. Other compound classes with surfactant properties such as proteins, humic acids, and synthetic detergents were also analyzed. Foam occurrence paralleled with saponin concentration and with the amounts of detached Ranunculus biomass accumulating at the dam of the hydroelectric power plant of Schaffhausen located just above the Rhine Fall but not with the concentration of synthetic detergents. The ecotoxicological potential of Ranunculus constituents, water, and foam samples was checked with a representative range of aquatic indicator organisms. No acute toxicity was observed at concentrations that were at least 50-fold higher than those found in the environmental samples.
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