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The present study aims to assess the removal of 3-amino-5-methylisoxazole (AMI), a recalcitrant by-product resulting from the biological breakdown of some pharmaceuticals, applying a solar photo-Fenton process assisted by ferrioxalate complexes (SPFF) (Fe 3+ /H 2 O 2 /oxalic acid/UVA-Vis) and classical solar photo-Fenton process (SPF) (Fe 2+ /H 2 O 2 /UVA-Vis). The oxidation ability of SPFF was evaluated at different iron/oxalate molar ratios (1:3, 1:6, and 1:9, with [total iron] = 3.58 × 10 −2  mM and [oxalic acid] = 1.07 × 10 −1 , 2.14 × 10 −1 and 3.22 × 10 −1  mM, respectively) and pH values (3.5–6.5), using low iron contents (2.0 mg Fe 3+ L −1 ). Additionally, the use of other organic ligands such as citrate and ethylenediamine-N,N′-disuccinic acid (EDDS) was tested. The oxidation power of the classical SPF was assessed at different pH values (2.8–4.0) using 2.0 mg Fe 2+ per liter. Furthermore, the effect of AMI concentration (2–20 mg L −1 ), presence of inorganic ions (Cl − , SO 4 2− , NO 3 − , HCO 3 − , NH 4 + ), and radical scavengers (sodium azide and D-mannitol) on the SPF method at pH 3.5 was also assessed. Experiments were done using a lab-scale photoreactor with a compound parabolic collector (CPC) under simulated solar radiation. A pilot-scale assay was conducted using the best operation conditions. While at near neutral pH, an iron/oxalate molar ratio of 1:9 led to the removal of 72 % of AMI after 90 min of SPFF, at pH 3.5, an iron/oxalate molar ratio of 1:3 was enough to achieve complete AMI degradation (below the detection limit) after 30 min of reaction. The SPF process at pH 3.5 underwent a slower AMI degradation, reaching total AMI degradation after 40 min of reaction. The scale up of SPF process showed a good reproducibility. Oxalic and oxamic acids were identified as the main low-molecular-weight carboxylic acids detected during the pilot-scale SPF reaction. Graphical abstract ᅟ

The main goal of this study was to evaluate the removal of bromate from drinking water using a heterogeneous photocatalytic mili-photoreactor, based on NETmix technology. The NETmix mili-reactor consists of a network of channels and chambers imprinted in a back slab made of acrylic (AS) or stainless steel (SSS) sealed, through mechanical compression and o-rings, with an UVA-transparent front borosilicate glass slab (BGS). A plate of UVA-LEDs was placed above the BGS window. TiO 2 -P25 thin films were immobilized on the BGS (back-side illumination, BSI) or SSS (front-side illumination, FSI) by using a spray deposition method. The photoreduction rate of a 200 μg L −1 (1.56 μM) BrO 3 − solution was assessed taking into account the following: (i) catalyst film thickness, (ii) catalyst coated surface and illumination mechanism (BSI or FSI), (iii) solution pH, (iv) type and dose of sacrificial agent (SA), (v) reactor material, and (vi) water matrix. In acidic conditions (pH 3.0) and in the absence of light/catalyst/SA, 28% and 36% of BrO 3 − was reduced into Br − only by contacting with AS and SSS during 2-h, respectively. This effect prevailed during BSI experiments, but not for FSI ones since back SSS was coated with the photocatalyst. The results obtained have demonstrated that (i) the molar rate of disappearance of bromates was similar to the molar rate of formation of bromides; (ii) higher BrO 3 − reduction efficiencies were reached in the presence of an SA using the FSI at pH 3.0; (iii) formic acid ([BrO 3 − ]:[CH 2 O 2 ] molar ratio of 1:3) presented higher performance than humic acids (HA = 1 mg C L −1 ) as SA; (iv) high amounts of HA impaired the BrO 3 − photoreduction reaction; (v) SSS coated catalyst surface revealed to be stable for at least 4 consecutive cycles, keeping its photonic efficiency. Under the best operating conditions (FSI, 18 mL of 2% wt. TiO 2 -P25 suspension, pH 3.0), the use of freshwater matrices led to (i) equal or higher reaction rates, when compared with a synthetic water in the absence of SA, and (ii) lower reaction rates, when compared with a synthetic water containing formic acid with a [BrO 3 − ]:[CH 2 O 2 ] molar ratio of 1:3. Notwithstanding, heterogeneous TiO 2 photocatalysis, using the NETmix mili-reactor can be used to promote the reduction of BrO 3 − into Br − , attaining concentrations below 10 μg L −1 (guideline value) after 2-h reaction. Graphical Abstract .

In the last decade, environmental risks associated with wastewater treatment plants (WWTPs) have become a concern in the scientific community due to the absence of specific legislation governing the occupational exposure limits (OEL) for microorganisms present in indoor air. Thus, it is necessary to develop techniques to effectively inactivate microorganisms present in the air of WWTPs facilities. In the present work, ultraviolet light A radiation was used as inactivation tool. The microbial population was not visibly reduced in the bioaerosol by ultraviolet light A (UVA) photolysis. The UVA photocatalytic process for the inactivation of microorganisms (bacteria and fungi, ATCC strains and isolates from indoor air samples of a WWTP) using titanium dioxide (TiO 2 P25) and zinc oxide (ZnO) was tested in both liquid-phase and airborne conditions. In the slurry conditions at liquid phase, P25 showed a better performance in inactivation. For this reason, gas-phase assays were performed in a tubular photoreactor packed with cellulose acetate monolithic structures coated with P25. The survival rate of microorganisms under study decreased with the catalyst load and the UVA exposure time. Inactivation of fungi was slower than resistant bacteria, followed by Gram-positive bacteria and Gram-negative bacteria. Graphical abstract Inactivation of fungi and bacteria in gas phase by photocatalitic process performed in a tubular photoreactor packed with cellulose acetate monolith structures coated with TiO 2

Contaminants of emerging concern (CECs) are released daily into surface water, and their recalcitrant properties often require tertiary treatment. Electrochemical oxidation (EO) is often used as an alternative way to eliminate these compounds from water, although the literature barely addresses the neurotoxic effects of residual by-products. Therefore, this study investigated the performance of EO in the removal of five CECs (alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine) and performed neurotoxicity evaluations of residual EO by-products in Wistar rat brain hippocampal slices. Platinum-coated titanium (Ti/Pt) and boron-doped diamond (BDD) electrodes were studied as anodes. Different current densities (13–75 A m -2 ), pH values (3–10), electrolyte dosages (NaCl), and matrix effects were assessed using municipal wastewater (MWW). The drugs were successfully degraded after 5 min of reaction for both the Ti/Pt and BDD electrodes when a current density of 75 A m -2 was applied. For Ti/Pt and BDD, neutral and acidic pH demonstrated better CEC removal performance, respectively. Compound degradation using MWW achieved 40% removal after 120 min for Ti/Pt and ranged between 33 and 52% for the BDD anode. For Ti/Pt, neurotoxicity studies using MWW indicated a decrease in reactive oxygen species (ROS) signals. However, when an artificial cerebrospinal fluid (ACSF) medium was reapplied, the signal recovered and increased to a value above the baseline, indicating that cells recovered part of their normal activity but remained in a different condition. For the BDD anode, the treated MWW did not cause significant ROS production variations, suggesting that he EO was effective in eliminating the toxicity of the treated solution.

The increasing prevalence of polystyrene nanoplastics (PSNPs) in aquatic environments poses significant risks due to their persistence and potential toxicity. Conventional water treatment methods have proven ineffective in removing these emerging pollutants, highlighting the urgent need for sustainable and efficient treatment. This study investigates the application of catalytic ozonation using natural pyrolusite (n-MnO2) and oxalic acid (OA) as a co-catalyst for the environmentally friendly degradation of PSNPs. Key operational parameters, including pH, applied ozone dose, pyrolusite dosage, and OA concentration, were systematically evaluated. Results demonstrate that the MnO2 + OA + O3 system enhances the generation of reactive oxygen species (ROS), leading to improved PSNP removal while maintaining the applied ozone dose compared to the single ozonation reaction. The highest TOC removal of 75% was achieved within 30 min of treatment under optimal conditions (pH = 4, [MnO2] = 0.5 g L−1, [OA] = 10 mg L−1, and ozone dose of 37.5 mg min−1), with significant turbidity reduction, indicating both chemical and physical degradation of PSNPs. Catalyst reusability after three consecutive cycles confirmed minimal loss in activity, reinforcing its potential as a sustainable catalytic system. These findings highlight natural MnO2-driven catalytic ozonation as a green and effective strategy for nanoplastic removal in water treatment applications.

In this study, an aqueous solution containing the azo dye Reactive Orange 16 (RO16) was subjected to two sequential treatment processes, namely: ozonation and biological treatment in a moving-bed biofilm reactor (MBBR). The most appropriate ozonation pretreatment conditions for the biological process and the toxicity of the by-products resulting from RO16 ozone oxidation were evaluated. The results showed that more than 97 % of color removal from the dye solutions with RO16 concentrations ranging from 25 to 100 mg/L was observed in 5 min of ozone exposure. However, the maximum total organic carbon removal achieved by ozonation was only 48 %, indicating partial mineralization of the dye. Eleven intermediate organic compounds resulting from ozone treatment of RO16 solution were identified by LC/MS analyses at different contact times. The toxicity of the dye-containing solution decreased after 2 min of ozonation, but increased at longer contact times. The results further demonstrated that the ozonolysis products did not affect the performance of the subsequent MBBR, which achieved an average chemical oxygen demand (COD) and ammonium removal of 93 ± 1 and 97 ± 2 %, respectively. A second MBBR system fed with non-ozonated dye-containing wastewater was run in parallel for comparison purposes. This reactor also showed an appreciable COD (90 ± 1 %) and ammonium removal (97 ± 2 %), but was not effective in removing color, which remained practically invariable over the system. The use of short ozonation times (5 min) and a compact MBBR has shown to be effective for the treatment of the simulated textile wastewater containing the RO16 azo dye.

This book presents recent developments in advanced biological treatment technologies that are attracting increasing attention or that have a high potential for large-scale application in the near future.It also explores the fundamental principles as well as the applicability of the engineered bioreactors in detail.

Pharmaceutically active compounds are carried into aquatic bodies along with domestic sewage, industrial and agricultural wastewater discharges. Psychotropic drugs, which can be toxic to the biota, have been detected in natural waters in different parts of the world. Conventional water treatments, such as activated sludge, do not properly remove these recalcitrant substances, so the development of processes able to eliminate these compounds becomes very important. Advanced oxidation processes are considered clean technologies, capable of achieving high rates of organic compounds degradation, and can be an efficient alternative to conventional treatments. In this study, the degradation of alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine was evaluated through TiO 2 /UV-A, H 2 O 2 /UV-A, and TiO 2 /H 2 O 2 /UV-A, using sunlight and artificial irradiation. While using TiO 2 in suspension, best results were found at [TiO 2 ] = 0.1 g L −1 . H 2 O 2 /UV-A displayed better results under acidic conditions, achieving from 60 to 80% of removal. When WWTP was used, degradation decreased around 50% for both processes, TiO 2 /UV-A and H 2 O 2 /UV-A, indicating a strong matrix effect. The combination of both processes was shown to be an adequate approach, since removal increased up to 90%. H 2 O 2 /UV-A was used for disinfecting the aqueous matrices, while mineralization was obtained by TiO 2 -photocatalysis.

The effect of salinity on the activity of nitrifying bacteria, floc characteristics, and microbial community structure accessed by fluorescent in situ hybridization and polymerase chain reaction-denaturing gradient gel electrophoresis techniques was investigated. Two sequencing batch reactors (SRB^sub 1^ and SBR^sub 2^) treating synthetic wastewater were subjected to increasing salt concentrations. In SBR^sub 1^, four salt concentrations (5, 10, 15, and 20 g NaCl/L) were tested, while in SBR^sub 2^, only two salt concentrations (10 and 20 g NaCl/L) were applied in a more shock-wise manner. The two different salt adaptation strategies caused different changes in microbial community structure, but did not change the nitrification performance, suggesting that regardless of the different nitrifying bacterial community present in the reactor, the nitrification process can be maintained stable within the salt range tested. Specific ammonium oxidation rates were more affected when salt increase was performed more rapidly and dropped 50% and 60% at 20 g NaCl/L for SBR^sub 1^ and SBR^sub 2^, respectively. A gradual increase in NaCl concentration had a positive effect on the settling properties (i.e., reduction of sludge volume index), although it caused a higher amount of suspended solids in the effluent. Higher organisms (e.g., protozoa, nematodes, and rotifers) as well as filamentous bacteria could not withstand the high salt concentrations. [PUBLICATION ABSTRACT]

This work highlights the performance of an ultrafiltration ceramic membrane as photocatalyst support and oxidant-catalyst/water contactor to promote sulfate radical advanced oxidation processes (SR-AOPs). Peroxydisulfate (PDS) activation mechanisms include photolysis (UVC irradiation) and chemical electron transfer (TiO 2 -P25 photocatalysis). The photoreactor is composed of an outer quartz tube (the “window”-radiation entrance to the reactor) and an inner tubular ceramic ultrafiltration membrane, where the catalyst particles (TiO 2 -P25) are immobilized on the membrane shell-side. PDS stock solution is fed by the lumen side of the membrane, delivering the oxidant to the catalyst particles and to the annular reaction zone (ARZ), being the catalyst and PDS activated by UV light. The design facilitates controlled radial slip of PDS into the catalyst surface and to concurrent water to be treated, flowing with a helix trajectory in the ARZ. Under continuous mode operation, with an UV fluence of 45 mJ cm −2 (residence time of 4.6 s), the UVC/PDS/TiO 2 system showed the best removal efficiency for two specific endocrine disrupting chemicals, 17β-estradiol (E2) and 17α-ethinylestradiol (EE2), spiked (100 μg L −1 each) in demineralized water and urban wastewater after secondary treatment. Graphical abstract