Graphene-Based Catalysts for Ozone Processes to Decontaminate Water.

The use of graphene-based materials as catalysts in both ozone and ozone/radiation processes is creating interest among researchers devoted to the study of advanced oxidation processes (AOPs) for the degradation of organic pollutants in water. In this review, detailed explanations of catalytic and photocatalytic ozonation processes mediated by graphene-based materials are presented, focusing on aspects related to the preparation and characterization of catalysts, the nature of the water pollutants treated, the type of reactors and radiation sources applied, the influence of the main operating variables, catalyst activity and stability, and kinetics and mechanisms.

Removal of Micropollutants in Water Reclamation by Membrane Filtration: Impact of Pretreatments and Adsorption.

Organic micropollutants (OMPs) present in water and wastewater are in the spotlight because of their potentially harmful effects even at low concentrations and the difficulties of their elimination in urban wastewater treatment plants (UWWTPs). This study explores the impact of some membrane filtration processes on the removal of a group of 11 OMPs with an eye on the effects of two pretreatments (i.e., coagulation and adsorption onto powdered activated carbon (PAC)) and the adsorption of OMPs onto the membranes on the overall removal. For this purpose, ultrafiltration (UF) and nanofiltration (NF) experiments were conducted with selected OMPs spiked in ultrapure water and secondary effluents from UWWTPs. It was observed that the adsorption of OMPs onto the membranes was influenced by the characteristics of the membranes, as well as the presence of effluent organic matter (EfOM). Since adsorption was the dominant mechanism for the rejection of OMPs by UF membranes, a study of the adsorption equilibrium of the micropollutants using UF membrane pieces as the adsorbent was conducted. The adsorption isotherms for the most hydrophobic OMPs fitted the Langmuir model. The efficiency of coagulation and powdered activated carbon (PAC) adsorption coupled with UF were also investigated. Both pretreatments alleviated membrane fouling and improved the rejection of organic and inorganic matter. The PAC pretreatment significantly improved the removal of OMPs in the combined PAC/UF process. The best options for achieving reclaimed water with satisfactory physicochemical quality, nearly devoid of OMPs and microorganisms, and suitable for diverse reuse purposes are either the NF treatment or the combination of PAC/UF.

Kinetic modelling of UVC and UVC/H2O2 oxidation of an aqueous mixture of antibiotics in a completely mixed batch photoreactor.

The removal kinetics of an aqueous mixture of thirteen antibiotics (i.e., ampicillin, cefuroxime, ciprofloxacin, flumequine, metronidazole, ofloxacin, oxytetracycline, sulfadimethoxine, sulfamethoxazole, sulfamethazine, tetracycline, trimethoprim and tylosin) by batch UVC and UVC/H2O2 processes has been modeled in this work. First, molar absorption coefficients (ε), direct quantum yields (Φ) and the rate constants of the reaction of antibiotics with hydroxyl radical (kHO•) (model inputs) were determined for each antibiotic and compared with literature data. The values of these parameters range from 0.3 to 21.8 mM-1 cm-1 for ε, < 0.01 to 67.8 mmol·E-1 for Φ and 3.8 × 109 to 1.7 × 1010 M-1 s-1 for kHO•. Second, a regression model was developed to compute the rate constants of the reactions of the antibiotics with singlet oxygen (k1O2) from experimental data obtained in batch UVC experiments treating a mixture of the antibiotics. k1O2 values in the 1-50 × 106 M-1 s-1 range were obtained for the antibiotics studied. Finally, a semi-empirical kinetic model comprising a set of ordinary differential equations was solved to simulate the evolution of the residual concentration of antibiotics and hydrogen peroxide (model outputs) in a completely mixed batch photoreactor. Model predictions were reasonably consistent with the experimental data. The kinetic model developed might be combined with computational fluid dynamics to predict process performance and energy consumption in UVC and UVC/H2O2 applications at full scale.

Mechanism considerations for photocatalytic oxidation, ozonation and photocatalytic ozonation of some pharmaceutical compounds in water.

Aqueous solutions of four pharmaceutical compounds, belonging to the group of emergent contaminants of water: atenolol (ATL), hydrochlorothiazide (HCT), ofloxacin (OFX) and trimethoprim (TMP), have been treated with different oxidation systems, mainly, photocatalytic oxidation, ozonation and photocatalytic ozonation. TiO2 has been used as semiconductor for photocatalytic reactions both in the presence of air, oxygen or ozone-oxygen gas mixtures. Black light lamps mainly emitting at 365 nm were the source of radiation. In all cases, the influence of some variables (concentrations of semiconductor, ozone gas and pharmaceuticals and pH) on the removal of pharmaceuticals, total polyphenol content (TPC) and total organic carbon (TOC) was investigated. A discussion on the possible routes of pharmaceutical and intermediates (as TPC and TOC) elimination has been developed. Thus, OFX TiO2/UVA degradation mechanism seems to develop through the participation of non-hydroxyl free radical species. Furthermore, the presence of OFX inhibits the formation of hydroxyl radicals in the photocatalytic process. The most effective processes were those involving ozone that lead to complete disappearance of parent compounds in less than 30 min for initial pharmaceutical concentrations lower than 2.5 mg L(-1). In the ozonation systems, regardless of the pH and the presence of TiO2, pharmaceuticals are degraded through their direct reaction with ozone. Photocatalytic ozonation was the most efficient process for TPC and TOC removals (≥ 80% and ≥60% elimination after 2 h of treatment, respectively) as well as in terms of the ozone consumption efficiency (1, 5.5 and 4 mol of ozone consumed per mol of TOC mineralized, at pH 4, 7 and 9, respectively). Weakly acid conditions (pH 4) resulted to be the most convenient ones for TPC and TOC removal by photocatalytic ozonation. This was likely due to formation of hydroxyl radicals through the ozonide generated at these conditions.

Solar photo-ozonation: A novel treatment method for the degradation of water pollutants.

The decomposition of aqueous ozone by UV-vis radiation has been investigated with focus on the impact of ozone photolysis on the degradation of water pollutants during solar ozonation processes. The apparent first-order rate constants of the decomposition of ozone (kobs) have been determined at various pHs in the 4-9 range using radiation of different wavelengths in the UV-vis range. It was found that UVA-visible radiation (λ>320nm) highly enhanced ozone decomposition, especially at pH 4, for which kobs was three-folded with respect to the process in the absence of radiation. Hydrogen peroxide was identified as a main intermediate of ozone photo-decomposition at pH 4. Experiments of degradation of oxalic acid by ozone showed that solar irradiation brings about an increase in the hydroxyl radical to ozone exposures ratio (Rct). Finally, photo-ozonation (λ>300nm) was shown advantageous over single ozonation in the mineralization of a selection of emerging contaminants (metoprolol, ibuprofen, N,N-diethyl-meta-toluamide and clofibric acid) in both ultrapure water and a synthetic secondary effluent. Thus, TOC removal in 2-h treatments increased from 10 to 25% in the absence of radiation to about 50% in the presence of radiation.

Insights into the removal of terbuthylazine from aqueous solution by several treatment methods.

This paper reports the removal of the s-triazine herbicide terbuthylazine (TBA) from aqueous solution by various treatment methods including adsorption onto activated carbon (AC) and multiwalled carbon nanotubes (MWCNT), UV254 photolysis, UV254/H2O2, single ozonation, O3/H2O2, catalytic ozonation (AC, MWCNT and TiO2 as catalysts) and some solar driven processes such as TiO2 photocatalytic oxidation and photo-ozonation. TBA was adsorbed onto AC and MWCNT following a pseudo-second order kinetics and Freundlich isotherm. Rapid small scale column tests showed that TBA could be removed from solution by adsorption onto AC better than atrazine. The UV254/H2O2 treatment resulted in excellent removal of TBA primarily due to the oxidation capability of hydroxyl radicals (kHO = 3.310(9) M(-1) s(-1)) generated from H2O2 photolysis. As the H2O2 initial concentration was increased from 5 to 50 mg L(-1) the HO exposure per UV fluence (RHO,UV) increased, making the process more efficient. Single ozonation also allowed complete removal of the herbicide though the process was slow (kO3=15.4 M(-1) s(-1) at pH > 4). The ozonation process could be greatly accelerated by the enhanced generation of HO through O3/H2O2 and O3/AC processes, which also led to more efficient processes in terms of ozone utilization. Commercial TiO2 (TiO2-P25) and lab prepared anatase TiO2 (TiO2-cat) nanoparticles catalyzed the removal of TBA by solar photocatalysis. In contrast, a lab prepared MWCNT-TiO2 composite was not useful as catalyst in solar photo-oxidation processes because of the HO scavenging nature of the MWCNT used as support. A mechanism for TBA degradation by O3 and HO has been suggested after TBA degradation intermediates identification.

Integration of ozonation and an anaerobic sequencing batch reactor (AnSBR) for the treatment of cherry stillage.

Cherry stillage is a high strength organic wastewater arising from the manufacture of alcoholic products by distillation of fermented cherries. It is made up of biorefractory polyphenols in addition to readily biodegradable organic matter. An anaerobic sequencing batch reactor (AnSBR) was used to treat cherry stillage at influent COD ranging from 5 to 50 g/L. Different cycle times were selected to test biomass organic loading rates (OLR(B)), from 0.3 to 1.2 g COD/g VSS.d. COD and TOC efficiency removals higher than 80% were achieved at influent COD up to 28.5 g/L but minimum OLR(B) tested. However, as a result of the temporary inhibition of acetogens and methanogens, volatile fatty acids (VFA) noticeably accumulated and methane production came to a transient standstill when operating at influent COD higher than 10 g/L. At these conditions, the AnSBR showed signs of instability and could not operate efficiently at OLR(B) higher than 0.3 g COD/g VSS.d. A feasible explanation for this inhibition is the presence of toxic polyphenols in cherry stillage. Thus, an ozonation step prior to the AnSBR was observed to be useful, since more than 75% of polyphenols could be removed by ozone. The integrated process was shown to be a suitable treatment technology as the following advantages compared to the single AnSBR treatment were observed: greater polyphenols and color removals, higher COD and TOC removal rates thus enabling the process to effectively operate at higher OLR, higher degree of biomethanation, and good stability with less risk of acidification.

Wet peroxide degradation of atrazine.

The high temperature (150-200 degrees C), high pressure (3.0-6.0 MPa) degradation of atrazine in aqueous solution has been studied. Under these extreme conditions atrazine steadily hydrolyses in the absence of oxidising agents. Additionally, oxygen partial pressure has been shown not to affect atrazine degradation rates. In no case mineralisation of the parent compound was observed. The addition of the free radical generator hydrogen peroxide to the reaction media significantly enhanced the depletion rate of atrazine. Moreover, partial mineralisation of the organics was observed when hydrogen peroxide was used. Again, oxygen presence did not influence the efficiency of the promoted reaction. Consecutive injections of hydrogen peroxide throughout the reaction period brought the total carbon content conversion to a maximum of 65-70% after 40 min of treatment (suggesting the total conversion of atrazine to cyanuric acid). Toxicity of the effluent measured in a luminometer decreased from 93% up to 23% of inhibition percentage. The process has been simulated by means of a semi-empirical model.

Solar photocatalytic ozonation of a mixture of pharmaceutical compounds in water.

Aqueous solutions of mixtures of four pharmaceutical compounds (atenolol, hydrochlorothiazide, ofloxacin and trimethoprim) both in Milli-Q ultrapure water and in a secondary effluent from a municipal wastewater treatment plant have been treated at pH 7 by different oxidation methods, such as conventional ozonation, photolytic ozonation, TiO2 catalytic ozonation, TiO2 photocatalytic oxidation and TiO2 photocatalytic ozonation. Experiments were carried out using a solar compound parabolic concentrator. The performance results have been compared in terms of removal of emerging contaminants (ECs), generation rate of phenolic intermediates, organic matter mineralization, ecotoxicity removal and enhancement of biodegradability. Also, the consumption of ozone to achieve certain treatment goals (95% removal of ECs and 40% mineralization) is discussed. Results reveal that solar photocatalytic ozonation is a promising oxidation method as it led to the best results in terms of EC mineralization (∼85%), toxicity removal (∼90%) and efficient use of ozone (∼2mgO3mgEC(-1) to achieve complete EC removal and ∼18mgO3mgTOC(-1) to achieve 40% EC mineralization, respectively).

TiO2 and Fe (III) photocatalytic ozonation processes of a mixture of emergent contaminants of water.

A mixture of three emergent contaminants: testosterone (TST), bisphenol A (BPA) and acetaminophen (AAP) has been treated with different photocatalytic oxidation systems. Homogeneous catalysts as Fe(III) alone or complexed with oxalate or citrate ions, heterogeneous catalysts as titania, and oxidants such as hydrogen peroxide and/or ozone have been used to constitute the oxidation systems. For the radiation type, black light lamps mainly emitting at 365 nm have been used. The effects of pH (3 and 6.5) have been investigated due to the importance of this variable both in ozone and Fe(III) systems. Removal of initial compounds and mineralization (total organic carbon: TOC) were followed among other parameters. For the initial compounds removal ozonation alone, in many cases, allows the highest elimination rates, regardless of the presence or absence of UVA light and catalyst. For mineralization, however, ozone photocatalytic processes clearly leads to the highest oxidation rates.

Granular activated carbon promoted ozonation of a food-processing secondary effluent.

This paper reports on the application of a simultaneous combination of ozone and a granular activated carbon (O(3)/GAC) as a tertiary treatment of a wastewater generated from the activity of various food-processing industries. Prior to the O(3)/GAC treatment, the wastewater was subjected to conventional primary and secondary treatments in a full-scale wastewater treatment plant (WWTP). The effluent from the WWTP presented high organic load (COD>500 mg/l and TOC>150 mg/l), which could be much reduced by the O(3)/GAC treatment. Results from the O(3)/GAC experiments were compared with those obtained in single ozonation, single adsorption onto GAC and sequential O(3)-GAC adsorption experiments. While single processes and the sequential one showed limited capacity to remove organic matter for the food-processing effluent (COD removal <40%), the simultaneous O(3)/GAC process led to decreases of COD up to 82% at the conditions here applied. The combined process also improved the ozone consumption, which decreased from about 19 g O(3)/g TOC (single ozonation process) to 8.2-10.7 g O(3)/g TOC (O(3)/GAC process). The reusability of the GAC throughout a series of consecutive O(3)/GAC experiments was studied with no apparent loss of activity for a neutral GAC (PZC = 6.7) but for a basic GAC (PZC = 9.1).

Mechanism and kinetic considerations of TOC removal from the powdered activated carbon ozonation of diclofenac aqueous solutions.

Ozonation of DCF in aqueous solution in the presence of powdered activated carbon (PAC) has been studied for mechanistic and kinetic purposes. The effects of gas flow rate, ozone gas concentration and initial TOC on the TOC elimination rate were then investigated. The use of PAC allows liquid-solid and internal diffusion mass transfer resistances being eliminated. Gas-liquid mass transfer resistance is also eliminated when ozonation is applied to DCF preozonated solutions. In the absence of mass transfer resistances a mechanism of reactions involving homogeneous and heterogeneous steps for TOC removal was proposed. From this mechanism a mathematical model constituted by mass balances of main species in water was established. Considerations about the changing nature of ozonation intermediates, as being promoters or inhibitors of ozone decomposition, is a key point to better predict the experimental concentrations of species present in this system.