Pyrrolizidine alkaloids (PAs) are persistent mutagenic and carcinogenic compounds produced by many common plant species. Health authorities recommend minimising human exposure via food and medicinal products to ensure consumer health and safety. However, there is little awareness that PAs can contaminate water resources. Therefore, no regulations exist to limit PAs in drinking water. This study measured a PA base concentration of ~ 70 ng/L in stream water adjacent to an invasive PA-producing plant Petasites hybridus (Asteraceae). After intense rain the PA concentration increased tenfold. In addition, PAs measured up to 230 ng/L in seepage water from groundwater wells. The dominant PAs in both water types corresponded to the most abundant PAs in the plants (senkirkine, senecionine, senecionine N-oxide). The study presents the first discovery of persistent plant toxins in well water and their associated risks. In addition, it for the first time reports monocrotaline and monocrotaline N-oxide in Petasites sp.

Background Ptaquiloside (PTA), caudatoside (CAU) and ptesculentoside (PTE) are carcinogenic illudane glycosides found in bracken ferns (Pteridium spp.) world-wide. The environmentally mobile PTA entails both acute and chronic toxicity and comparable risk might be associated with the structurally similar CAU and PTE. It is of great concern if these compounds are present in drinking water wells in bracken dominated regions, since they might pose a threat to human health. This study investigates the presence of PTA, CAU, PTE, and their corresponding hydrolysis products pterosins B (PtB), A (PtA) and G (PtG) in water wells in Denmark, Sweden and Spain. In total, 77 water samples from deep groundwater wells (40 – 100 m) and shallow water wells (8 – 40 m) were collected and preserved in the field, pre-concentrated in the laboratory and analysed by liquid chromatography-mass spectrometry (LC-MS). Results Deep groundwater wells contained neither illudane glycosides nor their pterosins. However, seven private shallow wells contained at least one of the illudane glycosides and/or pterosins at concentrations up to 0.27 µg L-1 (PTA), 0.75 µg L-1 (CAU), 0.05 µg L-1 (PtB), 0.03 µg L-1 (PtA) and 0.28 µg L-1 (PtG). Conclusions Detected concentrations of illudane glycosides in some of investigated wells exceeded the suggested maximum tolerable concentrations of PTA, although they were used for drinking water purpose. Contaminated wells were characterized by shallow depth, lower pH and electrical conductivity compared to deep groundwater wells where no illudane glycosides or pterosins were found.

Background Ptaquiloside (PTA), caudatoside (CAU) and ptesculentoside (PTE) are carcinogenic illudane glycosides found in bracken ferns (Pteridium spp.) world-wide. The environmentally mobile PTA entails both acute and chronic toxicity. A comparable risk might be associated with the structurally similar CAU and PTE. It is of great health concern if these compounds are present in drinking water, however, it is currently unknown if these compounds can detected in wells in bracken-dominated regions. This study investigates the presence of PTA, CAU, PTE, and their corresponding hydrolysis products pterosins B (PtB), A (PtA) and G (PtG) in water wells in Denmark, Sweden and Spain. Water samples from a total of 77 deep groundwater wells (40–100 m) and shallow water wells (8–40 m) were collected and preserved in the field, pre-concentrated in the laboratory and analysed by liquid chromatography–mass spectrometry (LC–MS). Results Deep groundwater wells contained neither illudane glycosides nor their pterosins. However, seven private shallow wells contained at least one of the illudane glycosides and/or pterosins at concentrations up to 0.27 µg L−1 (PTA), 0.75 µg L−1 (CAU), 0.05 µg L−1 (PtB), 0.03 µg L−1 (PtA) and 0.28 µg L−1 (PtG). This is the first finding of illudane glycosides and pterosins in drinking water wells. Conclusions Detected concentrations of illudane glycosides in some of investigated wells exceeded the suggested maximum tolerable concentrations of PTA, although they were used for drinking water purpose. Contaminated wells were shallow with neutral pH and lower electric conductivity compared to deep groundwater wells with no illudane glycosides nor pterosins.

Ptaquiloside (PTA) is a carcinogenic compound naturally occurring in bracken ferns (Pteridium aquilinum). It is highly water soluble and prone to leaching from topsoil to surface and groundwaters. Due to possible human exposure via drinking water, PTA is considered as an emerging contaminant. We present a sensitive and robust method for analysis of PTA and its degradation product pterosin B (PtB) in groundwater. The method comprises two steps: sample preservation at the field site followed by sample pre-concentration in the laboratory. The preservation step was developed by applying a Plackett–Burman experimental design testing the following variables: water type, pH, filtering, bottle type, storage temperature, transportation conditions and test time. The best sample preservation was obtained by using amber glass bottles, unfiltered solutions buffered at pH 6, transported without ice, stored at 4 °C and analysed within 48 h. The recovery was 94% to 100%. The sample purification step had a pre-concentration factor of 250, and the recovery percentages of the entire method were 85 ± 2 (PTA) and 91 ± 3 (PtB). The limits of detection (LOD) of the full method were 0.001 µg L−1 and 0.0001 µg L−1 for PTA and PtB, respectively. The method enables sensitive monitoring of PTA and PtB in groundwater. Carcinogenic PTA was detected in one groundwater well (0.35 µg L−1).

Highlights First study to investigate fate of phytotoxins in drinking water treatment. Biological sand filters removed bracken toxins and certain alkaloids. Pyrrolizidine alkaloids showed recalcitrant character in sand filters. Further investigation involving more advanced treatment are needed.