Aquatic occurrence of phytotoxins in small streams triggered by biogeography, vegetation growth stage, and precipitation

Highlights: • Phytotoxins are toxic plant secondary metabolites with unknown aquatic exposure. • In total 128 of them were screened in surface water samples and 39 of them confirmed. • Phytotoxins leach from the biosphere to the hydrosphere. • Their occurrence was rationalized by vegetation, seasonality and precipitation. • Phytotoxins' persistence and mobility partly explained aqueous exposure. Toxic plant secondary metabolites (PSMs), so-called phytotoxins, occur widely in plant species. Many of these phytotoxins have similar mobility, persistence, and toxicity properties in the environment as anthropogenic micropollutants, which increasingly contaminate surface waters. Although recent case studies have shown the aquatic relevance of phytotoxins, the overall exposure remains unknown. Therefore, we performed a detailed occurrence analysis covering 134 phytotoxins from 27 PSM classes. Water samples from seven small Swiss streams with catchment areas from 1.7 to 23 km² and varying land uses were gathered over several months to investigate seasonal impacts. They were complemented with samples from different biogeographical regions to cover variations in vegetation. A broad SPE-LC-HRMS/MS method was applied with limits of detection below 5 ng/L for over 80% of the 134 included phytotoxins. In total, we confirmed 39 phytotoxins belonging to 13 PSM classes, which corresponds to almost 30% of all included phytotoxins. Several alkaloids were regularly detected in the low ng/L-range, with average detection frequencies of 21%. This is consistent with the previously estimated persistence and mobility properties that indicated a high contamination potential. Coumarins were previously predicted to be unstable, however, detection frequencies were around 89%, and maximal concentrations up to 90 ng/L were measured for fraxetin produced by various trees. Overall, rainy weather conditions at full vegetation led to the highest total phytotoxin concentrations, which might potentially be most critical for aquatic organisms.