Multi-target assessment of advanced oxidation processes-based strategies for indirect potable reuse of tertiary wastewater: Fate of compounds of emerging concerns, microbial and ecotoxicological parameters.

Two advanced oxidation processes (AOPs), namely ozone/H2O2 and UV/H2O2, were tested at pilot scale as zero-liquid-discharge alternative treatments for the removal of microbiological (bacteria and viruses), chemical (compounds of emerging concern (CECs)) and genotoxic responses from tertiary municipal wastewater for indirect potable reuse (IPR). The AOP treated effluents were further subjected to granular activated carbon (GAC) adsorption and UV disinfection, following the concept of multiple treatment barriers. As a reference, a consolidated advanced wastewater treatment train consisting of ultrafiltration, UV disinfection, and reverse osmosis (RO) was also employed. The results showed that, for the same electrical energy applied, the ozone/H2O2 treatment was more effective than the UV/H2O2 treatment in removing CECs. Specifically, the ozone/H2O2 treatment, intensified by high pressure and high mixing, achieved an average CECs removal efficiency higher than UV/H2O2 (66.8% with respect to 18.4%). The subsequent GAC adsorption step, applied downstream the AOPs, further improved the removal efficiency of the whole treatment trains, achieving rates of 98.5% and 96.8% for the ozone/H2O2 and UV/H2O2 treatments, respectively. In contrast, the ultrafiltration step of the reference treatment train only achieved a removal percentage of 22.5%, which increased to 99% when reverse osmosis was used as the final step. Microbiological investigations showed that all three wastewater treatment lines displayed good performance in the complete removal of regulated and optional parameters according to both national and the European Directive 2020/2184. Only P. aeruginosa resulted resistant to all treatments with a higher removal by UV/H2O2 when higher UV dose was applied. In addition, E. coli STEC/VTEC and enteric viruses, were found to be completely removed in all tested treatments and no genotoxic activity was detected even after a 1000-fold concentration. The obtained results suggest that the investigated treatments are suitable for groundwater recharge to be used as a potable water source being such a procedure an IPR. The intensified ozone/H2O2 or UV/H2O2 treatments can be conveniently incorporated into a multi-barrier zero-liquid-discharge scheme, thus avoiding the management issues associated with the retentate of the conventional scheme that uses reverse osmosis. By including the chemical cost associated with using 11-12 mg/L of H2O2 in the cost calculations, the overall operational cost (energy plus chemical) required to achieve 50% average CECs removal in tertiary effluent for an hypothetical full-scale plant of 250 m3/h (or 25,000 inhabitants) was 0.183 €/m3 and 0.425 €/m3 for ozone/H2O2 and UV/H2O2 treatment train, respectively.

Optimal integration of vacuum UV with granular biofiltration for advanced wastewater treatment: Impact of process sequence on CECs removal and microbial ecology.

This study explored process synergies attainable by integrating a vacuum ultraviolet-based advanced oxidation process with biofiltration. A comparison using granular activated carbon or granular zeolite as filtration media were examined in context of advanced wastewater treatment for potable reuse. Six biofiltration columns, three with granular activated carbon and three with granular zeolite, were operated in parallel and batch-fed daily with nitrified secondary effluent. After achieving a pseudo-steady state through the filter columns, vacuum ultraviolet treatment was applied as pre-treatment or as post-treatment, at two different applied energies (i.e., VUV-E1=1 kWh/m3 and VUV-E10=10 kWh/m3). Once granular activated carbon had transitioned to biologically activated carbon, as determined based on soluble chemical oxygen demand removal, adsorption was still observed as the main mechanism for contaminants of emerging concern and nitrate removal. Vacuum ultraviolet pre-treatment markedly improved contaminants of emerging concern removal through the integrated system, achieving 40% at VUV-E1 and 90% at VUV-E10. When applied as post-treatment to zeolite column effluents, VUV-E1 and VUV-E10 further increased contaminants of emerging concern removal by 20% and 90%, respectively. In the zeolite system, vacuum ultraviolet pre-treatment also increased soluble chemical oxygen demand removal efficiency, indicating that higher energy vacuum ultraviolet increased biodegradability. Total prokaryotes were two-fold more abundant in biologically activated carbon than in zeolite, with vacuum ultraviolet pretreatment markedly affecting microbial diversity, both in terms of richness and composition. Media type only marginally affected microbial richness in the biofilters but showed a marked impact on structural composition. No clear relationship between compositional structure and depth was observed.

An innovative biofilter technology for reducing environmental spreading of emerging pollutants and odour emissions during municipal sewage treatment.

Wastewater treatment plants (WWTPs) are known sources of contaminants of emerging concern (CECs) spreading into the environment, as well as, of unpleasant odors. CECs represent a potential hazard for human health and the environment being pharmaceutical or biologically active compounds and they are acquiring relevance in European directives. Similarly, the public concern about odour emissions from WWTPs is also increasing due to the decreasing distance between WWTP and residential areas. This study focuses on the effectiveness of the recently developed MULESL technology (MUch LEss SLudge; WO2019097463) in removing CECs and limiting odour emissions from WWTPs. MULESL technology has been developed for its ability to reduce up to 80% the sludge production from WWTPs. However, it is ought to evaluate if the benefits coming from sludge production reduction do not invalidate CECs removal or negatively affect odour emissions. Thus, the performances of a MULESL and a conventional WWTP (flow rate of 375 m3/d and 3600 m3/d, respectively) were compared while treating the same municipal sewage. Whereas both plants succeeded in removing the traditional gross parameters characterizing wastewaters (e.g. chemical oxygen demand, nitrogen), the MULESL was much more effective than the conventional one in terms of CECs removal for about 60% of the identified compounds showing, however, the same or lower effectiveness for about 30% and 10% of them, respectively. This result was attributed to the high sludge retention time and biomass concentration in the MULESL (enabling enrichment of slow growing microorganisms and forcing biomass to use unusual substrates, respectively), and to the biomass feature to grow in the form of biofilm and granules (favoring micropollutants absorption on biomass). Furthermore, odour impact analysis has shown that the MULESL was characterized by a much lower impact, i.e. 45% lower than that of primary and secondary treatments of the conventional WWTP.

Degradation of emerging organic pollutants in wastewater effluents by electrochemical photocatalysis on nanostructured TiO2 meshes.

An immobilized photoactive TiO2 coating grown directly on titanium meshes was successfully exploited for the electrochemical photocatalytic degradation of carbamazepine in real secondary wastewater effluent. The catalyst was prepared by Plasma Electrolytic Oxidation and during the photocatalytic water treatment an electrical polarization (bias) was applied to the catalyst. The investigated process was compared with the conventional one employing suspended TiO2 powder (Degussa P25). Results showed that carbamazepine degradation rate follows the order UV/supported TiO2+bias ≈ UV/TiO2 Degussa P25 > UV/supported TiO2 > UV. The investigation also included the identification of other micropollutants and degradation products. This allowed the detection of 201 compounds present in the secondary wastewater effluent employed for the photocatalysis tests, 51 of them also successfully associated to compounds of emerging concern (CECs), and 194 to transformation products (TPs). The degradation of detected compounds followed first-order kinetics and the mean kinetic constant values of the 51 CECs resulted to be 0.048, 0.035 and 0.043 min-1 for the TiO2+Bias + UV, TiO2+UV and UV, respectively. As for TPs, results showed that the TiO2+Bias + UV treatment is much more efficient than both TiO2+UV and UV in minimizing the intensity of the organics in the real wastewater. Such a better performance was more pronounced at higher reaction time reaching 60% reduction of mean peak area of TPs at 90 min of reaction. Among the detected TPs also compounds belonging to known carbamazepine TPs were found. This allowed to propose a degradation pathway of carbamazepine. The supported catalyst was positively tested for 15 cycles demonstrating that it has the potential to be used in real wastewater tertiary steps aimed at removing CECs.

Identification of transformation products of carbamazepine in lettuce crops irrigated with Ultraviolet-C treated water.

Transformation of organic microcontaminants (OMCs) during wastewater treatments results in the generation of transformation products (TPs), which can be more persistent than parent compounds. Due to reuse of reclaimed wastewater (RWW) for crop irrigation, OMCs and TPs are released in soils being capable to translocate to crops. Furthermore, OMCs are also susceptible to transformation once they reach the soil or crops. The recalcitrant antiepileptic carbamazepine (CBZ) and some of its frequently reported TPs have been found in agricultural systems. However, there is no knowledge about the fate in reuse practices of multiple CBZ TPs that can be formed during wastewater treatment processes. For the first time, this work presents a study of the behavior of CBZ TPs generated after a conventional Ultraviolet-C (UVC) treatment in an agricultural environment. The UVC-treated water was used for the irrigation of lettuces grown under controlled conditions. The latter was compared to the fate of TPs generated in the peat and plant by irrigation with non-treated water containing CBZ. A suspect screening strategy was developed to identify the TPs using liquid chromatography coupled to quadrupole-time-of-flight (LC-QTOF-MS). The results revealed the presence of 24 TPs, 22 in UVC-treated water, 11 in peat and 9 in lettuce leaves. 4 of the TPs identified in peat (iminostilbene, TP 271B, TP 285A-B); and 3 in leaves (10-11 dihydrocarbamazepine, TP 271A-B) were not previously reported in soils or edible parts of crops, respectively. Comparing the TPs found in peat and lettuces derived from both irrigation conditions, no significant differences regarding TPs formation or occurrence were observed. UVC treatment did not contribute to the formation of different TPs than those generated by transformation or metabolism of CBZ in peat or plant material. This research improves the current knowledge on the fate of CBZ TPs in agricultural systems because of reuse practices.