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.

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.

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.

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 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.

The efficiency of TiO₂ as a catalyst in the ozonation of humic acid (HA) was evaluated in a comprehensive manner. Ozonation, catalytic ozonation and adsorption experiments were conducted using both synthetic HA solution and natural water. HA degradation was evaluated in terms of DOC, VIS₄₀₀ and UV₂₅₄. It was shown that the addition of catalyst positively affects the mechanism of ozonation. An increase in HA degradation was observed for all these parameters. The impact of catalyst dose and initial pH value of HA on the efficacy of catalytic ozonation was investigated. The highest removal efficiencies were achieved with the dose of 1 g l⁻¹ of TiO₂ (Degussa P-25) and in the acidic pH region. The catalytic ozonation process was efficient also on natural water component although not at the same level as it was on synthetic water. The adsorptive feature of P-25 was considered to have a clear evidence of the catalytic ozonation mechanism. The mechanism of catalysis on the surface of metal oxides was elucidated with the help of quantum-chemical calculations. In the framework of Density Function Theory (DFT), the O₃ decomposition was calculated in the catalytic and non-catalytic processes. Donor–acceptor properties of the frontier (highest occupied and lowest unoccupied molecular orbitals, HOMO/LUMO) orbitals are discussed. Electron density distribution and reaction mechanism of superoxide particles formation, which participate in the process of HA ozonation are analyzed.

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.

The purpose of this work was to study the efficiency of different treatments, based on the combination of O₃, H₂O₂, and TiO₂, on fresh surface water samples fortified with wild strains of Escherichia coli. Moreover, an exhaustive assessment of the influence of the different agents involved in the treatment has been carried out by kinetic modeling of E. coli inactivation results. The treatments studied were (i) ozonation (O₃), (ii) the peroxone system (O₃/0.04 mM H₂O₂), (iii) catalytic ozonation (O₃/1 g/L TiO₂), and (iv) a combined treatment of O₃/1 g/L TiO₂/0.04 mM H₂O₂. It was observed that the peroxone system achieved the highest levels of inactivation of E. coli, around 6.80 log after 10 min of contact time. Catalytic ozonation also obtained high levels of inactivation in a short period of time, reaching 6.22 log in 10 min. Both treatments, the peroxone system (O₃/H₂O₂) and catalytic ozonation (O₃/TiO₂), produced a higher inactivation rate of E. coli than ozonation (4.97 log after 10 min). While the combination of ozone with hydrogen peroxide or titanium dioxide thus produces an increase in the inactivation yield of E. coli regarding ozonation, the O₃/TiO₂/H₂O₂ combination did not enhance the inactivation results. The fitting of experimental values to the corresponding equations through non-linear regression techniques was carried out with Microsoft® Excel GInaFiT software. The inactivation results of E. coli did not respond to linear functions, and it was necessary to use mathematical models able to describe certain deviations in the bacterial inactivation processes. In this case, the inactivation results fit with mathematical models based on the hypothesis that the bacteria population is divided into two different subgroups with different degrees of resistance to treatments, for instance biphasic and biphasic with shoulder models.

We investigated the ozonation of the antineoplastic drugs cyclophosphamide (CP), ifosfamide (IF), and 5-fluorouracil (5-FU) and of the vasodilator pentoxifylline (PEN) in distilled water, in pharmaceutical wastewater, and in hospital effluent at pH 5–11. Under an alkaline pH of 11, all of the target compounds rapidly degraded through the attack of hydroxyl radicals, which resulted in their complete removal within 5 min at an ozone supply rate of 3 g O₃/h. Under acidic pH conditions, such as pH 5.6, CP and IF exhibited slower removal rates; however, compounds with unsaturated C-C bonds, such as 5-FU and PEN, were still removed at rapid rates under acidic conditions. Although the parent compounds were removed within minutes, the resulting ozonation byproducts were resistant to further ozonation and possessed increased Microtox acute toxicity. In distilled water, the resulting ozonation products exhibited minimal mineralization but high acute toxicity, whereas in naturally buffered pharmaceutical and hospital effluents, the byproducts were more amenable to removal and detoxification.

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.