Mixtures of chelating agents to enhance photo-Fenton process at natural pH: Influence of wastewater matrix on micropollutant removal and bacterial inactivation

Highlights: • Mixtures of fertilizers as complexing agents are effective in photo-Fenton process. • Process efficiency improvements are observed with organic fertilizers mixtures. • More than 70% of micropollutants abatement is achieved in MBR matrix with mixtures. • Higher iron release is observed in CAS matrix decreasing the process efficiency. • Suitability of treated effluents for their reuse in agriculture is reached. Three organic fertilizers (EDTA (Ethylenedinitrilotetraacetic acid), EDDS (Ethylenediamine-N, N′-disuccinic acid) and DTPA (Diethylene triamine pentaacetic acid)) were tested as Fe-complexes in photo-Fenton process at natural pH for micropollutants (MPs) abatement and simultaneous E.coli inactivation. Less stable Fe-complexes show high iron precipitation, stopping MPs degradation. On the contrary, stable Fe-complexes imply low kinetic rates for MPs removal. To solve these inconveniences, three mixtures of organic fertilizers were also tested, trying to improve the kinetic rates of micropollutants oxidation and overcome iron precipitation. Three different pollutants (propranolol (PROP), acetamiprid (ACMP) and sulfamethoxazole (SMX)) were used as the target compounds. As the iron release is, in part, linked to the hardness of water, two water matrices from two different secondary wastewaters (Membrane Bioreactor (MBR) and Conventional Activated Sludge (CAS)) were tested. The best performance in micropollutant degradation and E.coli inactivation was achieved with the combination of EDDS + EDTA, accomplishing a good equilibrium between iron precipitation and rate of MPs removal. For instance, total removal of propranolol was achieved at 45 min in MBR, while it was only 85.7% in CAS, being an improvement of the process comparing with that obtained using single organic fertilizers. At the end of the treatment, 2.1 log-inactivation for E.coli was reached in CAS. The differences observed between both wastewaters were related to CAS' higher DOC, turbidity, and hardness. Finally, from the physicochemical characterization conducted, including Biochemical Oxygen Demand at 5 days and phytotoxicity, it is possible to highlight the suitability of these treated effluents for its reuse in irrigation, as long as in CAS matrix the final values of E. coli are within the legal limit.