Organic and microbial contaminants of emerging concern (CECs), even though not yet regulated, are of great concern in reclaimed water reuse projects. Due to the large number of CECs and their different characteristics, it is useful to include only a limited number of them in monitoring programs. The selection of the most representative CECs is still a current and open question. This study presents a new methodology for this scope, in particular for the evaluation of the performance of a polishing treatment and the assessment of the risk for the environment and the irrigated crops. As to organic CECs, the methodology is based on four criteria (occurrence, persistence, bioaccumulation and toxicity) expressed in terms of surrogates (respectively, concentrations in the secondary effluent, removal achieved in conventional activated sludge systems, Log K_ow and predicted-no-effect concentration). It consists of: (i) development of a dataset including the CECs found in the secondary effluent, together with the corresponding values of surrogates found in the literature or by in-field investigations; (ii) normalization step with the assignment of a score between 1 (low environmental impact) and 5 (high environmental impact) to the different criteria based on threshold values set according to the literature and experts' judgement; (iii) CEC ranking according to their final score obtained as the sum of the specific scores; and (iv) selection of the representative CECs for the different needs. Regarding microbial CECs, the selection is based on their occurrence and their highest detection frequency in the secondary effluent and in the receiving water, the antibiotic consumption patterns, and recommendations by national and international organisations. The methodology was applied within the ongoing reuse project SERPIC resulting in a list of 30 indicator CECs, including amoxicillin, bisphenol A, ciprofloxacin, diclofenac, erythromycin, ibuprofen, iopromide, perfluorooctane sulfonate (PFOS), sulfamethoxazole, tetracycline, Escherichia coli, faecal coliform, 16S rRNA, sul1, and sul2.

This work provides a screening of organic contaminants and characterization of the dissolved organic matter in the sewer network until the municipal wastewater treatment plant (WWTP), identifying the network areas with a higher degree of contamination and their impact on the WWTP performance, particularly in the activated sludge reactor. Three monitoring campaigns were carried out at six selected locations of the sewage system (PVZ-1, PVZ-2, PS-F, PS-VC, CP-VC, and PS-T), influent (WWTP_INF) and effluent (WWTP_EFF) of the WWTP. Advanced analytical techniques were employed, namely excitation/emission matrix fluorescence-parallel factor analysis (EEM-PARAFAC), size exclusion chromatography with organic carbon detector (SEC-OCD), and liquid chromatography with high-resolution-mass spectrometric detection (LC-HRMS). EEM-PARAFAC showed higher fluorescence intensity for the protein-like component (C2), particularly at CP-VC (near seafood industries) associated with the presence of surfactants (~50 mg/L). SEC-OCD highlighted the WWTP efficiency in removing low molecular weight acids and neutrals. LC-HRMS tentatively identified 108 compounds of emerging concern (CEC) and similar detection patterns were obtained for all wastewater samples, except for PVZ-2 (lower detection), many of which occurred in the effluent. Eight CECs included on relevant Watch-Lists were detected in all WWTP_EFF samples. Furthermore, 111 surfactants were detected, the classes more frequently found being alcohol ethoxylates (AEOs), nonylphenol polyethoxylates (NPEOs) and linear alkylbenzene sulphonates (LAS). The continuous presence of LAS and NPEOs allied to surfactants concentrations in the WWTP_INF of 15-20 mg/L, with CP-VC location (linked with food industries) as an important contributor, explain the morphological changes in the activated sludge and high LAS content in the dewatered sludge, which may have impacted WWTP performance.