The potential of granular activated carbon (GAC) to remove iopromide and its intermediates from ozone-treated river water was evaluated. Mass spectrum analysis showed that ozone treatment lead to partial removal of iopromide (m/z 791.8) with generation of various intermediates. GAC demonstrated a lower iopromide adsorption (1.60 μg/g) in the presence of natural organic matter (NOM) compared to NOM-free water (12.54 μg/g), indicating the inhibitory effect of NOM on iopromide adsorption. Ozone treatment of the influent reduced the inhibitory effect of NOM by altering its composition and inducing polarity shift. GAC post-treatment resulted in improved removal of residual iopromide and its intermediates from the ozone-treated influent. Application of such combined treatment of ozonation followed by GAC adsorption can be an effective strategy for the removal of iopromide and its intermediates from contaminated water streams.

Ozone and ozone-based advanced oxidation processes were applied for the treatment of a recalcitrant wastewater generated by wood-based industries that contains different inorganic and organic constituents and high chemical oxygen demand (COD) varying between 3,400 and 4,000 mg/L. The investigation used a tubular ozone reactor combined with an UV reactor designed for different hydraulic retention times. The dependent variables addressed to evaluate the treatment efficiency were the reduction of COD and total organic carbon (TOC) and the biodegradability of the treated effluent based on respirometric studies using activated sludge from a wastewater treatment. The results showed that even though ozonation alone at acid pH promoted COD and TOC reductions of 65 and 31 % respectively, a decrease in the biodegradability was observed. The most effective treatment (COD and TOC reductions of 93 and 43 %, respectively) was obtained when applying ozone combined with UV light at basic pH. The ozone-UV combination was capable of increasing the amount of readily available COD by 75 % with an additional reduction of TOC by 60 %. In conclusion, ozonation at low pH effectively reduces the COD content in wastewater generated by the wood-based industry; however, in order to combine advanced oxidation with biological process, ozone combined with UV is recommended.

The elimination of five selected emerging contaminants (1-H-benzotriazole, N,N-diethyl-m-toluamide (DEET), chlorophene, 3-methylindole, and nortriptyline HCl) dissolved in different water matrices (surface water and secondary effluents) was carried out by sequential membrane filtration and chemical oxidation processes. First, a membrane filtration (ultrafiltration (UF) or nanofiltration(NF)) pre-treatment was conducted, and both permeate and retentate were afterwards treated by chemical oxidation, using ozone or chlorine. The application of UF and especially of NF provided a large volume of permeate, whose quality can be improved by a chemical treatment to completely remove residual contaminants except 1-H-benzotriazole. Chlorination and especially ozonation have demonstrated to be effective for the reduction of emerging contaminants in the concentrated stream, thus generating an effluent that might be recycled to the activated sludge treatment in the wastewater treatment plants (WWTP). In a second group of experiments, a chemical oxidation pre-treatment (by using ozone, chlorine, O₃/H₂O₂, ultraviolet (UV) radiation, or UV/H₂O₂) was applied followed by a nanofiltration process. Results of removals and rejection coefficients for the emerging contaminants showed that the chemical pre-treatment exerted a positive influence on the subsequent NF process, not only in terms of ECs removal but also of dissolved organic carbon content (DOC) reduction. While global removals higher than 97 % were reached for DEET, chlorophene, 3-methylindole, and nortriptyline HCl, lower values were obtained for 1-H-benzotriazole, especially for chlorine pre-treatment and in those water matrices with high content of natural organic matter. Therefore, both sequential treatments are promising to remove the selected micropollutants while reducing the chlorine doses needed to achieve final water disinfection.

This paper analyzes the mathematical modeling procedure to describe the decomposition of adsorbed phenanthrene in prototypical and real soil samples (sand and agricultural soil, respectively) by ozone. The modeling scheme considered a set of ordinary differential equations with time varying coefficients. This model used the adsorbed ozone in the soil, the ozone reacting with the contaminant and the phenanthrene concentration in the soil sample. The main parameters involved in the mathematical model included a time varying ozone saturation function (k ₛₐₜ (t)) and reaction constants (k ᵣ). These parameters were calculated using the ozone concentration variation at the reactor output, named as ozonogram, and the measurements of phenanthrene decomposition through ozonation. The model was validated using two series of experiments: (1) soil saturated with ozone in the absence of the contaminant and (2) soil artificially contaminated with phenanthrene. In both cases, the proposed parametric identification method yields to validate the mathematical model. This fact was confirmed by the correspondence between numerical simulations and experimental data. In particular, total decomposition of phenanthrene adsorbed in two different systems (ozone-sand and ozone-agricultural soil) was obtained after 15 and 30 min of reaction, respectively. This difference was obtained as a consequence of soil physicochemical characteristics: specific surface area and pore volume. The ozonation reaction rate constants of phenanthrene in the sand and agricultural soil were calculated using the same parameter identification scheme.

Catalytic ozonation process (COP) is a promising advanced oxidation process for petrochemical wastewater (PCW) treatment. However, the lack of economical and effective catalysts limits its application. Manganese sand ore (MSO) was utilized as a heterogeneous catalyst for ozonation of organic contaminants in PCW in this study. The calcined MSO-assisted COP (cMSO-COP) of aniline exhibited greater degradation than natural MSO-assisted COP or single ozonation process (SOP). The cMSO significantly promoted hydroxyl radical-mediated oxidation, decreased the ozonation activation energy by about 20 %, and doubled the reaction rates in comparison with SOP. The cMSO-COP increased the chemical oxygen demand (COD) removal of PCW twofold relative to SOP. The number of polar organic contaminants decreased by 50 % after cMSO-COP treatment. This study demonstrated the potential use of cMSO for efficient ozonation of petrochemical-derived contaminants at low cost.

Combination of ozone together with electrolysis (ozone-electrolysis) is a promising wastewater treatment technology. This work investigated the potential use of carbon nanotube (CNT)-based gas diffusion cathode (GDC) for ozone-electrolysis process employing hydroxyl radicals (·OH) production as an indicator. Compared with conventional active carbon (AC)-polytetrafluoroethylene (PTFE) and carbon black (CB)-PTFE cathodes, the production of ·OH in the coupled process was improved using CNTs-PTFE GDC. Appropriate addition of acetylene black (AB) and pore-forming agent Na₂SO₄ could enhance the efficiency of CNTs-PTFE GDC. The optimum GDC composition was obtained by response surface methodology (RSM) analysis and was determined as CNTs 31.2 wt%, PTFE 60.6 wt%, AB 3.5 wt%, and Na₂SO₄ 4.7 wt%. Moreover, the optimized CNT-based GDC exhibited much more effective than traditional Ti and graphite cathodes in Acid Orange 7 (AO7) mineralization and possessed the desirable stability without performance decay after ten times reaction. The comparison tests revealed that peroxone reaction was the main pathway of ·OH production in the present system, and cathodic reduction of ozone could significantly promote ·OH generation. These results suggested that application of CNT-based GDC offers considerable advantages in ozone-electrolysis of organic wastewater.

This study investigated the inactivation of two antibiotic resistance genes (ARGs)—sul1 and tetG, and the integrase gene of class 1 integrons—intI1 by chlorination, ultraviolet (UV), and ozonation disinfection. Inactivation of sul1, tetG, and intI1 underwent increased doses of three disinfectors, and chlorine disinfection achieved more inactivation of ARGs and intI1 genes (chlorine dose of 160 mg/L with contact time of 120 min for 2.98–3.24 log reductions of ARGs) than UV irradiation (UV dose of 12,477 mJ/cm²for 2.48–2.74 log reductions of ARGs) and ozonation disinfection (ozonation dose of 177.6 mg/L for 1.68–2.55 log reductions of ARGs). The 16S rDNA was more efficiently removed than ARGs by ozone disinfection. The relative abundance of selected genes (normalized to 16S rDNA) increased during ozonation and with low doses of UV and chlorine disinfection. Inactivation of sul1 and tetG showed strong positive correlations with the inactivation of intI1 genes (for sul1, R ² = 0.929 with p < 0.01; for tetG, R ² = 0.885 with p < 0.01). Compared to other technologies (ultraviolet disinfection, ozonation disinfection, Fenton oxidation, and coagulation), chlorination is an alternative method to remove ARGs from wastewater effluents. At a chlorine dose of 40 mg/L with 60 min contact time, the selected genes inactivation efficiency could reach 1.65–2.28 log, and the cost was estimated at 0.041 yuan/m³.

The objective of this work was to study the degradation and mineralization of ethylenethiourea (ETU) in water by ozonation at different pH values and in the presence of hydrogen peroxide. Degradation experiments were performed using an initial ETU concentration of 50 ppm for 180 min with a gas flux of 0.25 dm³ min⁻¹and an O₃production rate of 12.1 mg min⁻¹. Degradation of by-products was monitored by direct injection electrospray ionization mass spectrometry (ESI-MS), ETU concentration was determined by HPLC-UV, and its mineralization was detected by total organic carbon (TOC) analysis. Optimum degradation of ETU in water was observed at pH = 11, whereas at pH = 3, the degradation of ETU was slowest, indicating that the reaction occurred through different mechanisms. The additional effects of hydroxyl radicals formed at the highest pH can be used to explain the results obtained in this study. Peroxone experiments were carried out in the presence of 400 and 800 mg L⁻¹H₂O₂; the degradation of ETU was faster at 400 mg L⁻¹H₂O₂. This was attributed to the scavenging effect of the excess H₂O₂. ETU treatment by ozonation produced several by-products of degradation such as ethylene urea and 2-imidazoline.

The paper industry is adopting zero liquid effluent technologies to reduce freshwater use and meet environmental regulations, which implies closure of water circuits and the progressive accumulation of pollutants that must be removed before water reuse and final wastewater discharge. The traditional water treatment technologies that are used in paper mills (such as dissolved air flotation or biological treatment) are not able to remove recalcitrant contaminants. Therefore, advanced water treatment technologies, such as advanced oxidation processes (AOPs), are being included in industrial wastewater treatment chains aiming to either improve water biodegradability or its final quality. A comprehensive review of the current state of the art regarding the use of AOPs for the treatment of the organic load of effluents from the paper industry is herein addressed considering mature and emerging treatments for a sustainable water use in this sector. Wastewater composition, which is highly dependent on the raw materials being used in the mills, the selected AOP itself, and its combination with other technologies, will determine the viability of the treatment. In general, all AOPs have been reported to achieve good organic removal efficiencies (COD removal >40 %, and about an extra 20 % if AOPs are combined with biological stages). Particularly, ozonation has been the most extensively reported and successfully implemented AOP at an industrial scale for effluent treatment or reuse within pulp and paper mills, although Fenton processes (photo-Fenton particularly) have actually addressed better oxidative results (COD removal ≈ 65–75 %) at a lab scale, but still need further development at a large scale.

In this paper, Fe³⁺-doped TiO₂ nanotubes (Fe-TNTs) were successfully synthesized using hydrothermal method. Four different types of substrates, more specifically, ceramsite, zeolite, activated alumina, and activated carbon (AC), have been investigated in the study. The substrate-supported Fe-TNTs were used to effectively decompose humic acids (HAs) in water under O₃/UV conditions. The experiment results show that the highest photocatalytic activity was obtained in the presence of AC-supported 1.0 atomic percent (at.%) Fe-TNTs calcined at 500 °C, as HAs was removed by 97.4 %, with a pseudo-first-order rate constant of 0.126/min. The removal efficiencies of HAs reduced when the catalysts was repeatedly used, since the amount of adsorption sites of the supporting substrates decreased. However, even after the catalyst was repeatedly used for five times, the removal efficiency of HAs in the presence of AC-supported catalyst, which was 78.5 %, was still sufficient in water treatment. The enhanced photocatalytic activity of AC-supported Fe-TNTs was related to a synergistic effect of AC adsorption and Fe-TNT photocatalytic ozonation.