Changes in solution turbidity and color during paracetamol removal in laboratory and pilot-scale semicontinuous ozonation reactors.

Injecting ozone by means of a venturi device causes an increase in the mass transfer coefficient with respect to gas dissolution through a microdiffuser. Moreover, it was observed that significant turbidity levels are not formed (<1 NTU) when using a microdiffuser, probably due to the relatively high stirring which avoids formation of intermolecular hydrogen bonds. On the contrary, employing a venturi injector led to the production of high turbidity levels in water (up to 20 NTU). This indicates that formation of supramolecular structures causing this turbidity requires the presence of certain facilitating species which are formed through ozone decomposition mechanisms. The maximum ozone transfer takes place when operating at pH0 9.0, that is, when this value is close to the pKa and employing a dose of R = 115 mol O3/mol Pa0. Under these conditions, the degradation of paracetamol generates color, which is attributed to the presence of condensation products from pyrogallol, catechol, resorcinol, acetamide, oxalic acid and 4-aminophenol. Once paracetamol is fully degraded and solution turns colorless, turbidity grows (>20 NTU). This is attributed to formation of high molecular weight structures from 4-aminophenol and oxamide. Operating with large ozone excess (R = 500 mol O3/mol Pa0), the maximum ozone transfer rate is achieved at pH0 = 12.0. Under these conditions, the pollutant is fully removed together with water aromaticity and oxalic acid (able to form linear structures through hydrogen bonding) is detected during color development. Then, turbidity is formed due to cyclic dimer formation from acetic acid.

Reactions of bisphenol F and bisphenol S with ozone and hydroxyl radical: Kinetics and mechanisms.

Bisphenol F (BPF) and bisphenol S (BPS) are the most employed substitutes of bisphenol A (BPA), after being restricted by legislation in different countries because of its endocrine disrupting behaviour. In the present work, a deep study was performed about the reactivity of BPF and BPS with ozone and hydroxyl radical. Firstly, the second order rate constants of ozone with the di-protonated, mono-protonated and deprotonated species of both bisphenols were determined to be 2.38 × 104, 1.31 × 109 and 1.43 × 109 M-1 s-1 for BPF and 5.01, 2.82 × 107 and 1.09 × 109 M-1 s-1 for BPS. Then, the second order rate constants for the reaction of hydroxyl radical with BPF and BPS were established through UV/H2O2 and UV experiments at pH 7, resulting in the values of 8.60 × 109 and 6.60 × 109 M-1 s-1, respectively. Finally, a study regarding the transformation products (TPs) from the reaction of both bisphenols with molecular ozone and hydroxyl radical was also performed. Hydroxylation in the ortho position of the phenol rings was observed as main degradation pathway. Additionally, most of the TPs were accumulated over the reactions at relatively high oxidant doses.

Use of organic fertilizers in solar photo-Fenton process as potential technology to remove pineapple processing wastewater in Costa Rica.

Background: This work studied the use of the organic fertilizers DTPA-Fe and EDDS-Fe as iron chelates for solar driven photo-Fenton process at natural pH. This process was proposed to investigate its performance on removing a mixture of agrochemicals (propiconazole, imidacloprid and diuron) from pineapple processing wastewater to obtain a suitable effluent to be reused in the agricultural sector. Methods: Experiments were carried out in a solar simulator with a stirred cylindric photoreactor, with a volume of 150 mL and controlled temperature (20°C). The first set of experiments was carried out with ultrapure water to determine optimal iron and H 2O 2 concentrations. The second was performed with simulated wastewater of pineapple processing. Results: The optimized operational conditions for both iron complexes were 10 mg L -1 of Fe (III) and 25 mg L -1 of H 2O 2, since more than 80% of micropollutants (MP) (at an initial concentration of 1 mg L -1 of each compound) were removed in only 20 min with both DTPA-Fe and EDDS-Fe. The effect of organic matter and inorganic salts on radicals scavenging and chelates stability was also investigated in the experiments performed with synthetic pineapple processing wastewater. The results disclosed differences depending on the iron complex. Nitrites were the principal component influencing the tests carried out with EDDS-Fe. While carbonates at low concentration only significantly affected the experiments performed with DTPA-Fe, they were the major influence on the MPs removal efficiency decrease. In contrast, the presence of Ca 2+ and Mg 2+ only influence on this last one. Finally, the results of phytotoxicity disclosed the suitability of treated effluent to be reused in the agricultural sector.  Conclusions: This work demonstrated that solar powered photo-Fenton catalysed by iron fertilizer EDDS is a suitable technology for depolluting water streams coming from pineapple processing plants at circumneutral pH, and its subsequent reuse for crop irrigation.

Role of sunlight and oxygen on the performance of photo-Fenton process at near neutral pH using organic fertilizers as iron chelates.

Nowadays, reaction mechanisms of photo-Fenton process with chelated iron are not yet clearly defined. In this study, five organic fertilizers were used as iron complexes to investigate the role of sunlight and oxygen in photo-Fenton at near neutral pH. UV absorbance and stability constant of each selected iron chelate is different, and this work demonstrates that these parameters affect the reaction mechanisms in SMX degradation. Irradiation experiments without H2O2 revealed that only EDDS-Fe and DTPA-Fe achieved SMX degradation, but different iron release. These results, together with soluble oxygen free experiments, allowed the proposal of complementary reaction mechanisms to those of the classical photo-Fenton. The proposed mechanisms start through the potential photoexcitation of the iron complex, followed by subsequent oxygen-mediated hydroxyl radical generation reactions that are different for EDDS-Fe and DTPA-Fe. Moreover, irradiation experiments using EDTA-Fe and HEDTA-Fe had negligible SMX degradation despite iron release was observed, evidencing the differences between iron chelates.

Nitrosation and nitration of diclofenac and structurally related nonsteroidal anti-inflammatory drugs (NSAIDs) in nitrifying activated sludge.

Diclofenac (DCF) is a highly consumed non-steroidal anti-inflammatory drug that is excreted partially metabolized and is poorly removed during wastewater treatment. Previous findings demonstrated that DCF in wastewater treatment plants (WWTP) is partially removed to nitro/nitroso compounds. The reactive nitrogen species, that are microbially produced during nitrification in the activated sludge of WWTP, were suspected to be involved in the transformation of DCF. Therefore, here, we investigated the molecular features governing such biotransformation and the role played by nitrifying bacteria by biodegradation experiments at lab scale in enriched nitrifying sludge bioreactors spiked with DCF and other structurally related non-steroidal anti-inflammatory drugs (NSAIDs). We provided evidence of the incorporation of NO/NO2 groups into DCF originated from ammonia by isotopically labelled biodegradation experiments. Nitroso and nitro-derivatives were tentatively identified for all NSAIDs studied and biotransformation mechanisms were proposed. Our findings from biodegradation experiments performed under different incubation conditions suggested that biotransformation of DCF and its related NSAIDs might not only be microbially mediated by ammonia oxidizing bacteria, but other nitrifiers co-occurring in the activated sludge as ammonia oxidizing archaea and nitrite oxidizing bacteria. Follow-up studies should be conducted to disentangle such complex behaviour in order to improve removal of these contaminants in WWTPs.

Can ozone inactivate SARS-CoV-2? A review of mechanisms and performance on viruses.

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.

Coagulation-flocculation followed by catalytic ozonation processes for enhanced primary treatment during wet weather conditions.

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.

Application of solar-based oxidation to the management of empty pesticide container rinse water in Bolivia.

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 Fe 2+ 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 ([H 2O 2] 0 = 200 mg L -1) with Fe 2+ 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 Fe 2+ 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.

Photocatalytic degradation of sulfamethoxazole using TiO2 in simulated seawater: Evidence for direct formation of reactive halogen species and halogenated by-products.

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.

Continuous versus single H2O2 addition in peroxone process: Performance improvement and modelling in wastewater effluents.

Ozonation combined with continuous addition of H2O2 was studied as potential strategy for the effective abatement of ozone-resistant micropollutants from wastewater effluents. Oxidant doses within and beyond immediate ozone demand completion were tested. Through experiments involving the continuous addition of H2O2 in a semi-continuous 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 to single ozonation, representing a 28 % reduction in energy consumption. This improvement 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 (i.e., ROHO3 concept) calculation demonstrated that higher (0.5-1) and lower (0.25) oxidant relationships work better in improving the process performance during initial and secondary stages, respectively. Moreover, continuous versus total initial addition of H2O2 were compared and the first one showed better performance, representing differences in energy costs up to 21 %. Finally, two strategies for the real-time control of the O3-recalcitrant MPs fate were tested, one based on the ROHO3 concept and the other on UVA254 monitoring. Both resulted in accurate predictions (R2 > 0.96) for different compounds, effluents and processes.

Sunlight and UVC-254 irradiation induced photodegradation of organophosphorus pesticide dichlorvos in aqueous matrices.

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.