Application of a non-target workflow for the identification of specific contaminants using the example of the Nidda river basin

Non-target screening of water samples from the Nidda river basin in central Germany was conducted with the goal to identify previously unknown chemical contaminants and their emission sources. The focus was on organic, water-borne contaminants which were not typical to municipal wastewater. Grab samples of river water from 13 locations on the Nidda and 15 of its tributaries, in sum 112 samples, were analysed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances, features originating from the same compound such as adducts and isotopologues as well as in-source fragments and species with multiple charge states were registered and grouped by a componentization step utilizing both retention times and peak shapes of the features to combine them in a single component. This led to a reduction of the number of features by an average of 1235 per sample (46%). These grouped features were prioritized if these were detected only in specific tributaries or specific river sections, reducing the number of components by an average of 913 per sample (78%). In addition, grouped features were labelled as typically found in municipal wastewater by combining data from 16 wastewater treatment plants located across Germany and Switzerland and comparing this to components detected in the Nidda basin. These were removed, leading to a further reduction of components by an average of 72 per sample (30%) for an average total reduction of 2536 per sample (93%). Finally, nine compounds, with emission sources in three specific tributaries, were identified, including the textile additive Nylostab S-EED®, which was previously not known to be an environmental contaminant, as well as naturally occurring compounds such as highly toxic microcystins. [Display omitted] •A workflow was applied to localize emissions of organic contaminants within a river basin.•Annotation of data from contaminants ubiquitously present in municipal wastewater was applied.•Six industrial chemicals not previously observed in the aquatic environment were identified.