Artificial low-calorie sweeteners are consumed in considerable quantities with food and beverages. After ingestion, some sweeteners pass through the human metabolism largely unaffected, are quantitatively excreted via urine and feces, and thus reach the environment associated with domestic wastewater. Here, we document the widespread occurrence of four sweeteners in the aquatic environment and show that one of these compounds, acesulfame, meets all of the criteria of an ideal marker for the detection of domestic wastewater in natural waters, particularly groundwater. Acesulfame was consistently detected in untreated and treated wastewater (12-46 microg/L), in most surface waters, in 65% of the investigated groundwater samples, and even in several tap water samples (up to 2.6 microg/L) from Switzerland. The sweetener was not eliminated in wastewater treatment plants (WWTPs) and was quite persistent in surface waters, where concentrations increased with population in the catchment area and decreased with water throughflow. The highest concentrations in groundwater, up to 4.7 microg/L, were observed in areas with significant infiltration of river water, where the infiltrating water received considerable discharges from WWTPs. Given the currently achieved detection limit of approximately 0.01 microg/L, it is possible to trace the presence of > or = 0.05% wastewater in groundwater.
The mode of action of azole compounds implies a potential to affect endocrine systems of different organisms and is reason for environmental concern. The occurrence and fate of nine agricultural azole fungicides, some of them also used as biocides, and four azole pharmaceuticals were studied in wastewater treatment plants (WWTPs) and lakes in Switzerland. Two pharmaceuticals (fluconazole, clotrimazole, 10-110 ng L(-1)) and two biocides (propiconazole, tebuconazole, 1-30 ng L(-1)) were consistently observed in WWTP influents. Loads determined in untreated and treated wastewater indicated thatfluconazole, propiconazole, and tebuconazole were largely unaffected by wastewater treatment, but clotrimazole was effectively eliminated (> 80%). Incubation studies with activated sludge showed no degradation for fluconazole and clotrimazole within 24 h, but strong sorption of clotrimazole to activated sludge. Slow degradation and some sorption were observed for tebuconazole and propiconazole (degradation half-lives, 2-3 d). In lakes, fluconazole, propiconazole, and tebuconazole were detected at low nanogram-per-liter levels. Concentrations of the pharmaceutical fluconazole correlated with the expected contamination by domestic wastewater, but not those of the biocides. Per capita loads of propiconazole and tebuconazole in lakes suggested additional inputs; for example, from agricultural use or urban runoff rainwater.
Nicotine is extensively metabolized in the human body to a number of compounds, which may enter natural waters via discharge of domestic wastewater. However, little is known on exposure of and potential effects on the aquatic environment. In this study, two major urinary metabolites, cotinine and 3'-hydroxycotinine, as well as a further tobacco alkaloid, N-formylnornicotine, were measured in wastewater and water from Swiss lakes using an analytical procedure based on SPE and LC-MS/MS SRM with cotinine-d3 as internal standard (LOQs, 1.0-1.5 ng/L). Typical concentrations of cotinine and 3'-hydroxycotinine were approximately 1-10 microg/L in untreated wastewater, but clearly less in treated wastewater (approximately 0.01-0.6 microg/L), corresponding to elimination efficiencies of 90-99%. N-Formylnornicotine, however,was found at similar concentrations in untreated and treated wastewater (0.02-0.15 microg/L). Its apparent persistence during wastewater treatment was further confirmed by incubation experiments with activated sludge. In lakes, cotinine, 3'-hydroxycotinine, and N-formylnornicotine were detected at concentrations up to 15, 80, and 6 ng/L, respectively. Concentrations in lakes correlated with the expected anthropogenic burden by domestic wastewater (ratio population per water throughflow), demonstrating the suitability of these nicotine derivatives as hydrophilic, anthropogenic markers. In small receiving waters with significant wastewater discharges, concentrations of a few hundred ng/L may be expected. Possible ecotoxicological risks associated with such environmental concentrations, can, however, not be assessed at present as data on effects on aquatic organisms are very limited, in particular on long-term effects.
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