Emission of (chlorinated) reclaimed water into a Mediterranean River and its related effects to the dissolved organic matter fingerprint

Abstract

High resolution mass spectrometry (HRMS) was used to investigate the dissolved organic matter (DOM) profile of a reclamation water trial performed in the Llobregat River (Spain) during summer 2019. 23 water samples (including tertiary effluents, surface river and drinking water), taken during five sampling campaigns, were analyzed and their van Krevelen diagrams were compared. The reclaimed water fingerprint was substantially different from the natural profile of the river, showing a higher number of heteroatomic signals (i.e. CHON, CHOS and CHONS) and the presence of high-intensity S-containing features. As a result, reclaimed water discharge introduced substantial changes in the signature of the lignin-like and soot-like compositional-spaces of the river DOM fingerprint. However, the effect on the drinking water fingerprint was, ultimately, very limited. Only a limited number of features (up to 34) were detected as exclusively emitted with the reclaimed water.During the second phase of the trial, the tertiary effluent was chlorinated for disinfection purposes. This process triggered the unexpected formation of a myriad of new features along the Llobregat River. Notably, 109 brominated/chlorinated features were detected, probably generated as a consequence of the photochemical decay of the emitted chloramines and their free-radical reaction with DOM, and three of them persisted in the final drinking water. The formation of halogenated species in situ in the Llobregat River entails uncertainty at ecological and water treatment levels and should be studied carefully to fully disclose the risks associated to wastewater effluent disinfection.