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Paracetamol aqueous solutions, when ozonized, acquired a strong red coloration depending on the applied ozone dose and the initial pH of the aqueous solution. Then, this color loses intensity and turns to yellow. Color formation is favored when operating at initial pH0 = 12.0 and ozone flow-rate 4.2 mg/min. A mechanism describing color formation was proposed, being the main pathway involved an initial paracetamol hydroxylation to yield 3-hydroxyacetaminophen followed by the formation of 2-amino-5-hydroxyacetofenone. Then, these compounds are degraded to colored oxidation by-products. A model describing color evolution was also proposed, considering first-order kinetics for both color formation and degradation. The corresponding kinetic constant values were determined to be kf = 0.01 (1/min) and kd = 0.03 pH −0.055 (1/min), respectively. A relationship between aromaticity loss and color changes during the reaction has been estimated considering the parameter α=kA/kf, being α = 1.62 pH + 3.5 and the first-order rate constant for aromaticity loss given by kA = 0.0162 pH + 0.035 (1/min).

Background: The management of empty pesticide containers (EPC) in Bolivia has been recently promoted as a control strategy for dispersed pollution in surface and underground water bodies, as well as in soil. It comprises the rinsing and proper disposal or reuse of clean EPC. However, the rinsing transfers the hazard to water, which must be properly treated before being discharged. Methods: In this study, solar photo-Fenton at low Fe2+ doses were tested at pilot plant scale in Cochabamba (Bolivia) for the removal of pesticides dimethoate and atrazine in their commercial form, spiked in river water. Results: The results demonstrated that solar photo-Fenton ([H2O2]0 = 200 mg L-1) with Fe2+ concentrations between 0.5 and 1.5 mg L-1 is an effective method to remove dimethoate and atrazine, at an initial concentration of 10 mg L-1 each. Efficiency increased when increasing Fe2+ doses, achieving a removal over 99% of both pesticides after a solar irradiation period of 60 minutes (corresponding to an accumulated energy of 4.96 kJ L-1). Conclusions: The presence of high concentrations of natural components of river water, mainly organic and inorganic carbon species, would have contributed to hydroxyl radical scavenging, explaining, together with the low iron dose applied, the high energy (irradiation time) and high hydrogen peroxide concentration required to produce pesticide depletion. Additionally, the relatively low oxidant consumption and mineralization observed leave room for process optimization regarding oxidant and catalyst doses and warrant further studies on its coupling with biological or other post-treatments for the removal of transformation products.

Severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) pandemic has challenged societies around the globe. Technologies based on ozone, a powerful oxidant, have been evaluated to inactivate this virus in aerosols and fomites. However, the high data diversity hinders the possibility of establishing a common ground for determining best practices for the use of these technologies. Furthermore, there is a lack of consensus regarding which are the main mechanisms of ozone virus inactivation. This critical review examined the most relevant information available regarding ozone application in gas-phase for different viruses inactivation (including recent publications dealing with SARS-CoV-2), and pointed towards envelope alteration as the main reaction pathway for enveloped viruses, such as is the case of SARS-CoV-2. It could also be concluded that gaseous ozone can be indeed an effective disinfectant, successfully inactivating viruses such us influenza A H1N1, MERS-CoV, SARS-CoV-1 or even SARS-CoV-2 in aerosols or fomites. In reviewed works, low ozone exposures, just around 0.1–0.4 mg L-1 min, achieve about 4 log10 of inactivation in aerosols, while exposures between 1 and 4 mg L-1 min may be needed to guarantee an inactivation of 3–4 log10 in different fomites. Although further studies are required, ozone is an effective candidate to be used against SARS-CoV-2 or other viruses in surfaces and indoor locations., Graphical Abstract ga1

Nowadays photoactivation mechanism of titanium dioxide nanoparticles (TiO2 NPs) and reactive species involved in saline waters is not sufficiently established. In this study, TiO2 photocatalytic process under simulated solar irradiation was evaluated in synthetic seawater and compared with deionized water, using sulfamethoxazole (SMX) as model organic compound. For a TiO2 concentration of 100 mg L−1, SMX degradation resulted two times slower in seawater than in deionized water by the determination of their pseudo-first order rate constants of 0.020 min−1 and 0.041 min−1, respectively. Selected scavenging experiments revealed no significant contribution of hydroxyl radicals ( OH) on the degradation process in seawater, while these radicals contributed to circa 60% on the SMX depletion in deionized water. Instead, the involvement of reactive halogen species (RHS) as main contributors for the SMX degradation in seawater could be established. A mechanism for the RHS generation was proposed, whose initiation reactions involve halides with the TiO2 photogenerated holes, yielding chlorine and bromine radicals (Cl and Br ) that may later generate other RHS. Production of RHS was further confirmed by the identification of SMX transformation products (TPs) and their evolution over time, carried out by liquid chromatography-mass spectrometry (LC-MS). SMX transformation was conducted through halogenation, dimerization and oxidation pathways, involving mainly RHS. Most of the detected transformation products accumulated over time (up to 360 min of irradiation). These findings bring concerns about the viability of photocatalytic water treatments using TiO2 NPs in saline waters, as RHS could be yielded resulting in the generation and accumulation of halogenated organic byproducts.

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., The authors wish to thank the Ministry of Economy and Competitiveness of Spain (project CTQ2017-86466-R, MINECO/FEDER, UE), AGAUR-Generalitat de Catalunya (project 2017SGR-131) and Nuria López FPU research fellowship (FPU-16/02101) financed by Ministry of Science, Innovation and Universities of Spain.

The photo-Fenton process, with UV-A LED (λ = 380–390, 390–400 and 380–400 nm) has demonstrated to be effective in the abatement of a target micropollutant, such as diphenhydramine hydrochloride (DPH). Different concentrations of iron (Fe2+) and H2O2 were tested and monitored, and the best results in DPH removal were obtained for the highest concentrations of both iron (II) and H2O2 (10 mg Fe2+/L - 150 mg H2O2/L). The evolution of iron and peroxide concentration was also monitored. Kinetic studies showed that dark Fenton process prevails at the beginning of the experiment, when Fe2+ concentration is higher. However, after these initial moments, the prevailing process is photo-Fenton and, in addition, wavelength radiation plays an important role. Concerning the effect of radiation, four LEDs (4.2 W total power) were used, emitting radiation in the wavelength range between 380–390 or 390–400 nm. Similar results were obtained in both cases in DPH removal by photo-Fenton (30 min for total elimination). However, a synergistic effect was observed when two LEDs of 380–390 nm and two LEDs of 390–400 nm were used. Total power was the same (4.2 W) in each experimental condition, but the increase in the wavelength range to 20 nm (380–400 nm) produces an increase in the rate of DPH removal, achieving its total elimination at 15 min. This fact, with the use of a simple radiation model, reveals the important role that radiation plays in the photo-Fenton process. Finally, the formed intermediates were determined and some reaction pathways were proposed.

The extension of ozonation up to ozone (O3) doses beyond immediate ozone demand (IOD) completion combined with continuous addition of hydrogen peroxide (H2O2) was studied as potential strategy of treatment aimed to the effective abatement of ozone-resistant micropollutants (MPs) from wastewater effluents. Through experiments involving the continuous addition of H2O2 in a semi-continuous ozone contactor, it was demonstrated that this new approach could lead to a 36% reduction of the overall O3 needs for a constant H2O2/O3 molar ratio of 0.25 compared with single ozonation, representing a 28% reduction in the energy consumption. This improvement, however, was mainly attributed to H2O2 addition during the secondary ozonation stage, where the direct ozone demand becomes less important. The ¿OH-exposure per consumed ozone (ROHO3) calculation demonstrated that larger H2O2/O3 ratios (0.5-1) lead to a little improvement on oxidation performance during the IOD stage, whereas relationships of 0.25 work markedly better during the secondary stage of the process. Moreover, continuous versus total initial addition of H2O2 were compared and the first one showed better performance, with differences in estimated energy costs up to 21%. Finally, and since monitoring the fate of O3-recalcitrant MPs during the process is essential, two different strategies for the real-time control of the O3-recalcitrant MPs fate during the process were tested, one based on the ROHO3 concept and the other on continuous measurements of ultraviolet absorbance at 254 nm (UVA254). They both showed accurate predictions (R2 > 0.96) for different compounds, effluents and processes.

Combined sewer overflows (CSO), generated during the wet weather flow from the combination of the inflow and stormwater runoff in sewer system, result in an overflow of untreated wastewater from sewer system, which might ultimately contain different micropollutants (MPs). In this study, a coagulation-flocculation-sedimentation (CFS) pretreated CSO spiked with MPs was treated by catalytic ozonation using carbon, iron, and peroxide-based catalysts. The catalysts were characterized and their activity on MPs removal was studied at two different ozone (O3) doses (5 and 10 mg L−1). The effect of the treatment on the spiked CSO effluent was also assessed from the acute toxicity of the effluent using Microtox®, Yeast, and Macrophage cell-line toxicity assay tests. All the carbon-based catalysts showed large surface area, which was strongly influenced by the activation technique in the preparation of the catalysts. The CFS treatment strongly reduced the turbidity (≥60%) but had marginal effect on the UV254, dissolved organic carbon (DOC), and pH. Sludge Based Carbon (SBC) showed strong adsorption capacity (≥60% removal efficiency) for all MPs studied compared to other carbon and iron-based catalysts. Ozonation alone was effective for the degradation of easily oxidizable MPs (sulfamethoxazole, mecoprop, and 2,4-dichlorophenoxyl acetic acid), achieving more than 80% degradation efficiency at 10 mg L−1 of ozone, but not effective for atrazine (≤60% degradation efficiency) at similar O3 dose. Catalytic ozonation (at 10 mg L−1 O3 dose) improved the degradation of the MPs at low catalyst dosage but higher dosage strongly inhibited their degradation. In all cases, the effluents showed negligible acute toxicity, indicating the suitability of the process for the treatment of CSO.

Nowadays, the industry is quite commonly using nanoparticles of titanium dioxide (nTiO2) especially in sunscreens, due to its higher reflective index in comparison to micron size TiO2. Its high demand causes its widespread environmental occurrence, thus damaging the environment. The aquatic ecosystems are the most vulnerable to contamination by nTiO2. Like other engineered nanoparticles, nTiO2 has demonstrated generation of reactive oxygen species (ROS) and reactive halogen species (RHS) in the aquatic environment under UV radiation. This study investigated the toxicity of nTiO2 towards two aquatic indicator organisms, one from freshwater (Daphnia magna) and the other from seawater (Artemia sp.), under simulated solar radiation (SSR). Daphnia magna and Artemia sp. were co-exposed in 16 h SSR and 8 h darkness cycles to different concentrations of nTiO2. The estimated EC50 at 48 h for D. magna was 3.16 mg nTiO2/L, whereas for A. sp. no toxic effects were observed. When we exposed these two organisms simultaneously to 48 h of prolonged SSR using higher nTiO2 concentrations, EC50 values of 7.60 mg/L and 5.59 mg/L nTiO2 for D. magna and A. sp., respectively, were obtained. A complementary bioassay was carried out with A. sp., by exposing this organism to a mixture of nTiO2 and organic UV filters (benzophenone 3 (oxybenzone, BP3), octocrylene (OC), and ethyl 4-aminobenzoate (EtPABA)), and then exposed to SSR. The results suggested that nTiO2 could potentially have negative impacts on these organisms, also this work outlines the different characteristics and interactions that may contribute to the mechanisms of environmental (in salted and freshwater) phototoxicity of nTiO2 and UV radiation, besides their interaction with organic compounds., Authors acknowledge the financial support of the Spanish Ministry of Science and Innovation, for projects ROUSSEAU (CTM2017-89767-C3-1-R), CEX2018-000794-S, and CTQ2017-86466-R., and AGAUR-Gencat project 2017SGR131. A.C. Soler acknowledges Mexican CONACyT for her doctoral grant (Ref. 409154).

The treatability of waters contaminated with priority pesticide dichlorvos (DDVP) by means of ozonation has been assessed for the first time. In order to do so, reaction kinetics, transformation mechanisms and associated toxicity have been inspected in detail. Second-order rate constants of DDVP reactions with O 3 and OH were determined to be 590 and 2.2·10 9 M −1 s −1 , respectively. These values partly explained the degradation profiles obtained during experiments with and without the presence of an OH scavenger, in which the significant contribution of the indirect degradative route in the removal of DDVP was revealed. LC-MS analyses for ozonated samples allowed the elucidation of desmethyl dichlorvos (d-DDVP), dichloroacetic acid (DCA) and dimethyl phosphate (DMP) as main transformation products (TPs). DMP was found to be present in both O 3 and OH -mediated oxidation pathways. Three possible degradation routes were proposed for OH degradation, whereas the direct oxidation by O 3 was only well-explained by the addition of this oxidant to the double bond of DDVP dichlorovinyl moiety. Microtox® bioassays revealed the inability of molecular ozone to reduce the toxicity of the medium and pointed out the importance of OH contribution in the degradation process. In general, ozonation could be a suitable treatment alternative for DDVP, formed TPs and associated toxicity abatement.

Despite the high toxicity and resistance to conventional water treatments exhibited by methiocarb (MC), there are no reports regarding the degradation of this priority pesticide by means of alternative purification technologies. In this work, the removal of MC by means of ozonation was studied for the first time, employing a multi-reactor methodology and neutral pH conditions. The second-order rate constants of MC reaction with molecular ozone (O3) and formed hydroxyl radicals (OH·) were determined to be 1.7·106 and 8.2·109 M−1 s−1, respectively. During degradation experiments, direct ozone reaction was observed to effectively remove MC, but not its formed intermediates, whereas OH· could oxidize all species. The major identified TPs were methiocarb sulfoxide (MCX), methiocarb sulfoxide phenol (MCXP) and methiocarb sulfone phenol (MCNP), all of them formed through MC oxidation by O3 or OH· in combination with hydrolysis. A toxicity assessment evidenced a strong dependence on MCX concentration, even at very low values. Despite the OH· capability to degrade MC and its main metabolites, the relative resistance of TPs towards ozone attack enlarged the oxidant dosage (2.5 mg O3/mg DOC) necessary to achieve a relatively low toxicity of the medium. Even though ozonation could be a suitable technique for MC removal from water compartments, strategies aimed to further promote the indirect contribution of hydroxyl radicals during this process should be explored.

Dichlorvos (DDVP) is an organophosphorus pesticide that has been classified as highly hazardous chemical by the World Health organization. In this study, the fate of the pesticide DDVP in natural water compartments was examined under simulated sunlight. Moreover, the effect of UV-254 irradiation on DDVP depletion was also studied. In deionized water, DDVP was photodegraded only in the presence of dissolved molecular oxygen. The photodegradation during the first 6 h of sunlight irradiation occurred with pseudo first-order kinetics, and the rate constants were 0.040 h−1 at pH 7 and 0.064 h−1 at pH 3. A reaction mechanism for the generation of reactive oxygen species (ROS) via DDVP photoabsorption was proposed. Humic acids (HA) played a double role as photosensitizer and inhibitor, observing an enhancement on DDVP photodegradation at low HA concentration (TOC = 2 mg L−1). The depletion of DDVP under 254 nm UV irradiation was ascribed to direct photodegradation and oxygen mediated photoinduced reactions. Direct photodegradation of DDVP decreased with 254 nm irradiation reduction, highlighting the importance of radical mediated mechanisms at low irradiation doses. Based on LC/MS data, the main photoproducts under simulated solar light and UV-C irradiation were identified and potential reaction pathways were postulated. The three main identified products were o-methyl 2,2-dichlorovinyl phosphate, dichloroacetaldehyde and dimethylphosphate. Moreover, the toxicity of samples was evaluated along the irradiation exposure time using Microtox® assays. This study brings new insights into the role of oxygen in the photodegradation of DDVP and the induced and inhibition mechanisms involved in the presence of the humic acids in natural waters. Fil: Bustos, Nahuel Jano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Unidad Ejecutora de Investigaciones en Producción Animal. Universidad de Buenos Aires. Facultad de Ciencias Veterinarias. Unidad Ejecutora de Investigaciones en Producción Animal; Argentina Fil: Cruz Alcalde, Alberto. Universidad de Barcelona; España Fil: Iriel, Analia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Unidad Ejecutora de Investigaciones en Producción Animal. Universidad de Buenos Aires. Facultad de Ciencias Veterinarias. Unidad Ejecutora de Investigaciones en Producción Animal; Argentina Fil: Fernandez Cirelli, Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Unidad Ejecutora de Investigaciones en Producción Animal. Universidad de Buenos Aires. Facultad de Ciencias Veterinarias. Unidad Ejecutora de Investigaciones en Producción Animal; Argentina Fil: Sans, Carmen. Universidad de Barcelona; España