A Rational Analysis on Key Parameters Ruling Zerovalent Iron-Based Treatment Trains: Towards the Separation of Reductive from Oxidative Phases.

The development of treatment trains for pollutant degradation employing zerovalent iron has been attracting a lot of interest in the last few years. This approach consists of pre-treatment only with zerovalent iron, followed by a Fenton oxidation taking advantage of the iron ions released in the first step. In this work, the advantages/disadvantages of this strategy were studied employing commercial zerovalent iron microparticles (mZVI). The effect of the initial amount of mZVI, H2O2, pH, conductivity, anions and dissolved oxygen were analysed using p-nitrobenzoic acid (PNBA) as model pollutant. 83% reduction of PNBA 6 µM into p-aminobenzoic acid (PABA) was achieved in natural water at an initial pH 3.0 and 1.4 g/L of mZVI, under aerobic conditions, in 2 h. An evaluation of the convenience of removing mZVI after the reductive phase before the Fenton oxidation was investigated together with mZVI reusability. The Fenton step against the more reactive PABA required 50 mg/L of H2O2 to achieve more than 96% removal in 15 min at pH 7.5 (final pH from the reductive step). At least one complete reuse cycle (reduction/oxidation) was achieved with the separated mZVI. This approach might be interesting to treat wastewater containing pollutants initially resistant to hydroxyl radicals.

Aluminized surface to improve solar light absorption in open reactors: Application for micropollutants removal in effluents from municipal wastewater treatment plants.

This work proposes the evaluation of an aluminized surface on the bottom of open reactors to perform a photo-Fenton process, at circumneutral pH (using Fe III-Ethylenediamine-N,N'-disuccinic acid complex), for elimination of micropollutants (MPs) in real effluents from municipal wastewater treatment plants (EMWWTP). Firstly, the strategy was to initially investigate the real EMWWTP spiked with several MPs (acetaminophen, diclofenac, carbamazepine, caffeine, trimethoprim and sulfamethoxazole) with 20 and 100 µg L-1 in a laboratory scale (evaluated by HPLC-UV) using a solar simulator. Finally, the removal of all MCs present in the real EMWWTP was monitored (evaluated by HPLC-MS) in a pilot-scale (90 L) in a raceway pond reactor (RPR). The treatment time required for degradation above 80% for the investigated MPs was over 30 min, and the predominant effect could be mainly associated with organics present in the real EMWWTP due to the light attenuation and scavenging of radical species. Moreover, the results confirmed that chloride and sulfate would most likely equally not affect the process. The use of an aluminized surface on the bottom of RPRs has been confirmed as a suitable option to improve the photo-Fenton reaction, enabling the use of lower doses of iron. Up to 60 different MPs found in EMWWTP have been successfully degraded using 0.1 mM of Fe at circumneutral pH with a consumption of 30 mg L-1 H2O2 with less than 45 min.

Olive mill wastewater reuse to enable solar photo-Fenton-like processes for the elimination of priority substances in municipal wastewater treatment plant effluents.

Olive mill wastewater (OMW) appears as an interesting and innovative natural alternative to synthetic chelating agents of iron in solar photo-Fenton processes at circumneutral pH due to its high polyphenol content, valorizing wastewater typically found in sunny countries. The aim of this work was the reuse of OMW for the elimination of other recalcitrant microcontaminants: terbutryn, chlorfenvinphos, diclofenac, and pentachlorophenol. Highly diluted OMW (1:1500) was employed to keep the iron in solution at circumneutral pH. Eighty percent degradation of microcontaminants was achieved, although the reaction rate was slow compared with conventional photo-Fenton process, due to Fe-polyphenol complex instability at neutral pH. At pH around 4 (considerable superior to the photo-Fenton optimal pH 2.8), Fe-polyphenol complex stability was promoted: solar UV energy required was 25 times lower to reach the objective of 80% microcontaminants degradation, which was attained in a single step, without coupling with other processes. Operating photo-Fenton at slightly acidic pH was proposed for the first time for possible reuse of treated wastewater in crop irrigation, requiring minimum pH adjustment by simply mixing it with natural wastewater. Graphical abstract.

Advanced treatment of urban wastewater by UV-C/free chlorine process: Micro-pollutants removal and effect of UV-C radiation on trihalomethanes formation.

The effect of the UV-C/free chlorine (FC) process on the removal of contaminants of emerging concern (CECs) from real urban wastewater as well as the effect of UV-C radiation on the formation of trihalomethanes (THMs) compared to FC process alone was investigated. Unlike of FC process, UV-C/FC was really effective in the degradation of the target CECs (carbamazepine (CBZ), diclofenac, sulfamethoxazole and imidacloprid) in real wastewater (87% degradation of total CECs within 60 min, QUVC = 1.33 kJ L-1), being CBZ the most refractory one (49.5%, after 60 min). The UV-C radiation significantly affected the formation of THMs. THMs concentration (mainly chloroform) was lower in UV-C/FC process after 30 min treatment (<1 µgL-1 = limit of quantification (LOQ)) than in FC process in dark (2.3 µgL-1). Noteworthy, while in FC treated wastewater chloroform concentration increased after treatment, UV-C/FC process resulted in a significant decrease (residual concentrations below the LOQ), even after 24 h and 48 h post-treatment incubation. The formation of radicals due to UV-C/FC process can reduce THMs compared to chlorination process, because part of FC reacts with UV-C radiation to form radicals and it is no longer available to form THMs. These results are encouraging in terms of possible use of UV-C/FC process as advanced treatment of urban wastewater even for possible effluent reuse.

Contaminants of emerging concern removal from real wastewater by UV/free chlorine process: A comparison with solar/free chlorine and UV/H2O2 at pilot scale.

The removal of contaminants of emerging concern (CECs) from urban wastewater treatment plants (UWTPs) is really important to minimize the risk for human health and environment. In this study, the homogeneous advanced oxidation process (AOP) UV-C/free chlorine (UV-C/FC) was investigated at pilot scale in the degradation of a mixture of four CECs, in different water matrices and compared to a consolidated AOP, namely UV-C/H2O2. As matter of fact 90% degradation of CECs was observed after 15 min (QUVC = 0.33 kJ L-1) by UV-C/FC (5 mg L-1 of FC) and 30 min (0.67 kJ L-1) by UV-C/H2O2 (5 mg L-1 of H2O2) in natural water. However, CECs degradation by UV-C/H2O2 and UV-C/FC was comparable (>82%) in wastewater samples, under the investigated conditions (60 min, 1.33 kJ L-1). The effect of sunlight/FC process on the target CECs was also investigated (in a compound parabolic collector based reactor). Interestingly, a different behaviour was observed between the two light sources. In particular, a total removal of carbamazepine (CBZ) and imidacloprid (IMD) was observed for UV-C/FC process with 0.27 kJ L-1 and 10 mgL-1 of FC, while, in the sunlight/FC process (same FC dose), CBZ total removal took place quite fast (0.50 kJ L-1), but 90% removal of IMD was observed only after 60 min (7.09 kJ L-1). In conclusion, UV-C/FC process can be an interesting solution for tertiary treatment of urban wastewater for the removal of CECs and sunlight/FC is worthy of further investigation to evaluate its possible application in small UWTPs.