Degradation of selected pharmaceuticals in aqueous solution with UV and UV/H2O2

The degradation of four pharmaceutical compounds (PhACs), ibuprofen (IBU), diphenhydramine (DP), phenazone (PZ), and phenytoin (PHT) was investigated via ultraviolet (UV) photolysis and UV/H₂O₂ process with a low-pressure (LP) UV lamp. For each PhAC tested, direct photolysis quantum yields at 254 nm were found to be ranging from 6.32 × 10⁻² to 2.79 × 10⁻¹ mol E⁻¹ at pH 7. The second-order rate constants of the reaction between the PhACs and OH were determined to be from 4.86 × 10⁹ to 6.67 × 10⁹ M⁻¹ s⁻¹ by using a competition kinetic model which utilized para-chlorobenzoic acid (pCBA) as a reference compound. The overall effect of OH radical scavenging from humic acid (HA) and anions HCO₃⁻, NO₃⁻ was measured utilizing R_OH,UV method through examining the aqueous photodegradation of pCBA as a probe compound. Moreover, these fundamental direct and indirect photolysis parameters were applied in the model prediction for oxidation rate constants of the PhACs in UV/H₂O₂ process. It was found that the predicted oxidation rate constants approximated the observed ones. The results indicated that the new R_OH,UV probe compound method was applicable for measuring background OH radical scavenging effects in water treatment process of UV/H₂O₂. Furthermore, by GC-MS analysis, most of the intermediates created during the photodegradation of the selected PhACs in UV/H₂O₂ process were identified. For the photodegradation of PZ, a competition mechanism existed between the direct UV photolysis and the oxidation of OH. An appropriate dosage of H₂O₂ could hinder the occurrence of the direct photolysis.     

Gamma irradiation of pharmaceutical compounds, nitroimidazoles, as a new alternative for water treatment

The main objectives of this study were: (1) to investigate the decomposition and mineralization of nitroimidazoles (Metronidazole [MNZ], Dimetridazole [DMZ], and Tinidazole [TNZ]) in waste and drinking water using gamma irradiation; (2) to study the decomposition kinetics of these nitroimidazoles; and (3) to evaluate the efficacy of nitroimidazole removal using radical promoters and scavengers. The results obtained showed that nitroimidazole concentrations decreased with increasing absorbed dose. No differences in irradiation kinetic constant were detected for any nitroimidazole studied (0.0014-0.0017 Gy⁻¹). The decomposition yield was higher under acidic conditions than in neutral and alkaline media. Results obtained showed that, at appropriate concentrations, H₂O₂ accelerates MNZ degradation by generating additional HO; however, when the dosage of H₂O₂ exceeds the optimal concentration, the efficacy of MNZ degradation is reduced. The presence of t-BuOH (HO radical scavenger) and thiourea (HO, H and e_aq⁻ scavenger) reduced the MNZ irradiation rate, indicating that degradation of this pollutant can take place via two pathways: oxidation by HO radicals and reduction by e_aq⁻ and H. MNZ removal rate was slightly lower in subterranean and surface waters than in ultrapure water and was markedly lower in wastewater. Regardless of the water chemical composition, MNZ gamma irradiation can achieve i) a decrease in the concentration of dissolved organic carbon, and ii) a reduction in the toxicity of the system with higher gamma absorbed dose.     

Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater

Three tertiary-treated wastewater effluents were evaluated to determine the impact of wastewater quality (i.e. effluent organic matter (EfOM), nitrite, and alkalinity) on ozone (O₃) decomposition and subsequent removal of 31 organic contaminants including endocrine disrupting compounds, pharmaceuticals, and personal care products. The O₃ dose was normalized based upon total organic carbon (TOC) and nitrite to allow comparison between the different wastewaters with respect to O₃ decomposition. EfOM with higher molecular weight components underwent greater transformation, which corresponded to increased O₃ decomposition when compared on a TOC basis. Hydroxyl radical (OH) exposure, measured by parachlorobenzoic acid (pCBA), showed that limited OH was available for contaminant destruction during the initial stage of O₃ decomposition (t < 30 s) due to the effect of the scavenging by the water quality. Advanced oxidation using O₃ and hydrogen peroxide did not increase the net production of OH compared to O₃ under the conditions studied. EfOM reactivity impacted the removal of trace contaminants when evaluated based on the O₃:TOC ratio. Trace contaminants with second order reaction rate constants with O₃ (kO3) > 10⁵ M⁻¹ s⁻¹ and OH (k_OH) > 10⁹ M⁻¹ s⁻¹, including carbamazepine, diclofenac, naproxen, sulfamethoxazole, and triclosan, were >95% removed independent of water quality when the O₃ exposure () was measurable (0-0.8 mg min/L). O₃ exposure would be a conservative surrogate to assess the removal of trace contaminants that are fast-reacting with O₃. Removal of contaminants with and k_OH > 10⁹ M⁻¹ s⁻¹, including atrazine, iopromide, diazepam, and ibuprofen, varied when O₃ exposure could not be measured, and appeared to be dependent upon the compound specific k_OH. Atrazine, diazepam, ibuprofen and iopromide provided excellent linear correlation with pCBA (R² > 0.86) making them good indicators of OH availability.     

Incorporation of initiation, promotion and inhibition in the Rct concept and its application in determining the initiation and inhibition capacities of natural water in ozonation

Ozonation is widely employed in water treatment to purify water. The R_ct concept, which is defined as the ratio of OH exposure to ozone exposure, has been commonly used to quantify the OH concentration generating from ozone decomposition and model the removal of organic pollutant. Due to its empirical nature, however, the R_ct concept is limited in quantitatively elucidating how initiator, promoter and inhibitor involved in the OH chain reactions affect its value. A new R_ct model was developed by integrating the R_ct concept and the transient steady-state OH concentration to evaluate the influences of these modes of reactions on the R_ct value. It was found that the R_ct value is not only the ratio of OH exposure to ozone exposure but also the ratio of the total initiation capacity to the total inhibition capacity in a system. The presence of promoter, however, does not affect the R_ct value although it does accelerate ozone decomposition leading to lower ozone and OH exposures and result in hindered removal of target pollutant. The hindered removal of ibuprofen by ozonation in the presence of methanol (promoter) can be quantitatively described by the new R_ct model. The model can also be used to quantify the initiation and inhibition capacities of an ozonation system via the addition of an external inhibitor. Its application in determining the initiation and inhibition capacities of natural water was demonstrated.     

Evaluation of enhanced coagulation pretreatment to improve ozone oxidation efficiency in wastewater

Enhanced coagulation (EC) using ferric chloride was evaluated as a pretreatment process to improve the efficiency of ozone (O₃) for the oxidation of trace organic contaminants in wastewater. At the applied dosages (10-30 mg/L as Fe), EC pretreatment removed between 10 and 47% of the dissolved organic carbon (DOC) from the three wastewaters studied. Size exclusion chromatography (SEC) showed that EC preferentially removed higher apparent molecular weight (AMW) compounds. Subsequent O₃ testing was performed using an O₃:DOC ratio of 1. Results showed that O₃ exposures were similar even though the required doses were reduced by 10-47% by the EC pretreatment process. Hydroxyl radical (HO) exposure, measured by parachlorobenzoic acid (pCBA), showed 10% reduction when using a FeCl₃ dose of 30 mg/L, likely due to the lower O₃ dose and decreased production of HO during the initial phase of O₃ decomposition (t < 30 s). The oxidation of 13 trace organic contaminants (including atenolol, carbamazepine, DEET, diclofenac, dilantin, gemfibrozil, ibuprofen, meprobamate, naproxen, primidone, sulfamethoxazole, triclosan, and trimethoprim) was evaluated after EC and O₃ treatment. EC was ineffective at removing any of the contaminants, while O₃ oxidation reduced the concentration of compounds according to their reaction rate constants with O₃ and HO.     

The effect of nitrate, bicarbonate and natural organic matter on the degradation of sunscreen agent p-aminobenzoic acid by simulated solar irradiation

Our experiments revealed that a model sunscreen agent, p-aminobenzoic acid (PABA), can be effectively transformed through reactions that are mediated by simulated solar irradiation. We systematically explored the effects of nitrate ions, bicarbonate and different types of natural organic matter (NOM) on the degradation of PABA by simulated solar irradiation. Experimental data suggest that these components ubiquitous in nature water have different influence on the rates of the photoinduced removal of PABA. Products were extracted and analyzed using LC/MS and a total of four products probably resulting from OH and NO₂ radicals attack were identified and the possible reaction pathways were proposed. The findings in this study provide useful information for understanding the environmental transformation of sunscreen agent in aquatic system.     

Effectiveness of different oxidizing agents for removing sodium dodecylbenzenesulphonate in aqueous systems

The present study investigates the efficacy of various oxidizing treatments (ClO⁻, ClO₂, KMnO₄, O₃, O₃/H₂O₂, O₃/activated carbon) to remove from waters sodium dodecylbenzenesulphonate (SDBS), considered as model surfactant. Results obtained show that the use of ClO⁻ and ClO₂ does not cause appreciable SDBS degradation. Additionally, in the case of ClO⁻, trihalomethanes are generated, increasing system toxicity. Because the reaction kinetics between SDBS and KMnO₄ is very slow, a decrease in contaminant concentration is not observed, even at very acid pH values. SDBS reactivity with ozone is very low, with a kinetic constant (kO3) of 3.68 M⁻¹ s⁻¹, but its reactivity with HO radicals is very high (k_OH = 1.16 × 10¹⁰ M⁻¹ s⁻¹), therefore O₃/H₂O₂ and O₃/activated carbon, which can also generate HO, appear as promising advanced oxidation processes to remove this contaminant from waters. The method based on ozone and activated carbon was the only process studied that produced both an increase in SDBS removal rate (due to the generation of HO radicals in the O₃-PAC or O₃-GAC interaction) and a considerable reduction in the concentration of dissolved organic carbon in the system due to the PAC adsorbent properties.     

Photochemical fate of atorvastatin (lipitor) in simulated natural waters

Cholesterol-lowering statin drugs are among the most frequently prescribed for reducing human blood cholesterol and they have been detected as contaminants in natural waters. In this study the photochemical behavior of atorvastatin (lipitor) was investigated at two different concentrations of 35.8 μM (20 mg L⁻¹) and 35.8 nM (20 μg L⁻¹) using a solar simulator and a UV reactor. Photochemical fate in natural waters can be described in most cases by the sum of the loss due to hydrolysis, direct photolysis, and, reaction with hydroxyl radical (OH), singlet oxygen (¹O₂) (or O₂ (¹D)), and excited state dissolved organic matter (DOM). The absolute bimolecular reaction rate constant with OH was measured, using pulsed radiolysis, (1.19 ± 0.04) × 10¹⁰ M⁻¹ s⁻¹. The reaction rate constant of ¹O₂ was determined to be (3.1 ± 0.2) × 10⁸ M⁻¹ s⁻¹. Under the experimental conditions used, at high atorvastatin concentration (35.8 μM) the contribution of singlet oxygen (¹O₂) to the photodegradation of atorvastatin in natural waters was higher than that of hydroxyl radical, and accounted for up to 23% of the loss in aqueous solutions. Whereas, at a concentration of 35.8 nM, ¹O₂ (and OH) both played a minor role in the removal of this compound. Lastly, it also appears that atorvastatin reacts with ³DOM* contributing to its loss in simulated natural waters.     

Semicontinuous Fenton oxidation of phenol in aqueous solution. A kinetic study

This work investigates the Fenton oxidation of phenol in a semicontinuous reactor where the overall amount of H₂O₂ is distributed as a continuous feed upon the reaction time. The experiments were carried out at 25 °C and atmospheric pressure, with 100 mg/L initial phenol concentration and iron dosages from 1 to 100 mg/L. H₂O₂ aqueous solution was continuously fed during 4 h reaction time up to an overall dose varying within the range of 500-5000 mg/L. The results in terms of evolution of phenol, H₂O₂ and intermediates, as well as TOC abatement were compared with those obtained in conventional batch operation. It was found that the oxidation rates for phenol and intermediates were lower when adding the H₂O₂ continuously. However, a higher abatement of TOC was reached at the end of the 4-h reaction time, in spite of a similar overall H₂O₂ consumption. This is the result of a more efficient OH generation throughout the semicontinuous process, favouring the reaction with the organic species and reducing the occurrence of competitive scavenging reactions involving Fe²⁺, H₂O₂ and OH. Two kinetic models were proposed, one for describing the evolution of phenol, aromatics and H₂O₂ and the other for TOC. The influence of the operating conditions on the kinetic constants was also studied, looking for the optimal conditions in terms of both, environmental and economic points of view.     

Assessment of the UV/chlorine process as an advanced oxidation process

Several organic compounds were used as radical scavengers/reagents to investigate the possibility of the UV/chlorine process being used as an advanced oxidation process (AOP) in the treatment of drinking water and wastewater. The UV/H₂O₂ process was selected as a reference, so that the results from the UV/chlorine process could be compared with those of the UV/H₂O₂ process. Methanol was added to active chlorine solutions at both pH 5 and 10 and into hydrogen peroxide samples. The photodegradation quantum yields and the OH radical production yield factors, which are significant in evaluating AOPs, were calculated for both the UV/chlorine and the UV/H₂O₂ processes. The yield factor for the UV/chlorine process at pH 5 was 0.46 ± 0.09, which is much lower than that of the UV/H₂O₂ process, which reached 0.85 ± 0.04. In addition to methanol, para-chlorobenzoic acid (pCBA) and cyclohexanoic acid (CHA) were added to active chlorine solutions and to H₂O₂ solutions, to evaluate the efficiencies of oxidizing these organic compounds. The specific first-order reaction rate constants for the oxidation of pCBA and CHA, using the UV/chlorine process, were lower than those found using the UV/H₂O₂ process.     

Solar photo-Fenton degradation of nalidixic acid in waters and wastewaters of different composition. Analytical assessment by LC-TOF-MS

This work assessed the solar photo-Fenton degradation of nalidixic acid (NXA), a quinolone antibacterial agent, in several different aqueous solutions. It has been proven that the composition of the water clearly affects the efficiency of the photo-Fenton process. The presence of chlorine ions induces the concurrence of different mechanisms involving Cl and Cl₂⁻ radicals, which slow down the process. Up to 35 transformation products (TPs) were identified and their structures characterized by accurate LC-TOF-MS mass measurements during treatment of the different model waters. Photocatalytic degradation was thus observed to proceed mainly through the attack of the hydroxyl radicals on the double bond C₍₂₎C₍₃₎ which induce further ring opening. All the TPs identified persisted after total degradation of NXA. NXA in real pharmaceutical effluent was treated by photo-Fenton as a first stage before biological treatment. As NXA has been demonstrated to be recalcitrant to biological treatment, photo-Fenton treatment of the effluent was continued until its total degradation. Although NXA was efficiently degraded, LC-MS analyses demonstrated that some of the TPs identified after the photo-Fenton treatment were also recalcitrant to biological treatment, persisting after the combined treatment. These results show that analytical assessment of photocatalytic water treatments is essential to assure they are functioning as intended.     

The effect of electrode material on the generation of oxidants and microbial inactivation in the electrochemical disinfection processes

Electrochemical disinfection has gained increasing attention as an alternative for conventional drinking water treatment due to its high effectiveness and environmental compatibility. The most common method of electrochemical disinfection is the use of electro-generated oxidants, such as active chlorine and reactive oxygen species, as disinfectants. This study examined the role of electrode material on the generation of oxidants, and elucidated the different reaction pathways for generating individual oxidants by employing boron-doped diamond (BDD), Ti/RuO₂, Ti/IrO₂, Ti/Pt-IrO₂, and Pt as anode materials. The efficiency of OH production, as determined by para-chlorobenzoic acid (pCBA) degradation, was in the order of BDD ? Ti/RuO₂ ≈ Pt. No significant production of OH was observed at Ti/IrO₂ and Ti/Pt-IrO₂. The OH was found to play a key role in O₃ generation at BDD, but not at the other electrodes. The production of active chlorine was in the order of Ti/IrO₂ > Ti/RuO₂ > Ti/Pt-IrO₂ > BDD > Pt. The large difference in this order from that of ROS was attributed to the difference in the electrocatalytic activity of each electrode material toward the production of active chlorine, as evidenced by linear sweep voltammetry (LSV) measurements. In addition, the characteristics of microbial inactivation as a function of electrode material were examined under the presence of an inert electrolyte, using Escherichia coli as an indicator microorganism.     

Trimethoprim: kinetic and mechanistic considerations in photochemical environmental fate and AOP treatment

Trimethoprim (TMP), a bacteriostatic antibiotic, has recently been detected in wastewater and surface waters. In this study the sunlight mediated photochemical fate, and treatment using advanced oxidation and reduction (free radical) processes, have been investigated with respect to their effect on TMP. Photochemical fate, in the presence of humic acid, and advanced oxidation treatment both involve the hydroxyl radical (OH) as one of the reactive species of interest. Another reactive oxygen species, singlet oxygen (¹O₂), may also be important in the photochemical fate of TMP. The bimolecular reaction rate constants of TMP with ¹O₂ and OH were evaluated to be (3.2 ± 0.2) × 10⁶ M⁻¹ s⁻¹ and 8.66 × 10⁹ M⁻¹ s⁻¹, respectively. The reaction kinetics for the sub-structural moieties of TMP, 1,2,3-trimethoxybenzene (TMBz) and 2,4-diaminoprimidine (DAP), was evaluated to facilitate an understanding of the loss mechanisms. For TMBz and DAP the reaction rate constants with ¹O₂ were <1.0 × 10⁴ and (3.0 ± 0.1) × 10⁶ M⁻¹ s⁻¹, while with OH they were 8.12 × 10⁹ and 1.64 × 10⁹ M⁻¹ s⁻¹, respectively. The data suggests that the ¹O₂ attacks the DAP and the OH radical attacks the TMBz moiety. However, for TMP, ¹O₂ and OH reactions accounted for only ∼19% and ∼6%, of its total photodegradation, respectively. Therefore, the reaction of TMP with excited state natural organic matter is postulated as a significant degradation pathway for the loss of TMP in sunlit waters containing natural organic matter. There was no effect of pH on the direct or indirect photolysis of TMP. To complete the study for reductive treatment processes, the solvated electron reaction rates for the destruction of TMP, TMBz and DAP were also evaluated. The absolute bimolecular reaction rates obtained were, (13.6 ± 0.01) × 10⁹, (6.36 ± 0.11) × 10⁷ and (10.1 ± 0.01) × 10⁹ M⁻¹ s⁻¹, respectively.     

Ozone oxidation for the alleviation of membrane fouling by natural organic matter: A review

Membrane fouling by natural organic matter is one of the main problems that slow down the application of membrane technology in water treatment. O₃ is able to efficiently change the physico-chemical characteristics of natural organic matter in order to reduce membrane fouling. This paper presents the state-of-the-art knowledge of the reaction mechanisms between natural organic matter and molecular O₃ or OH radicals, together with an in-depth discussion of the interactions between natural organic matter and membranes that govern membrane fouling, inclusive the effect of O₃ oxidation on it.     

Efficient removal of microcystin-LR by UV-C/H₂O₂ in synthetic and natural water samples

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H₂O₂ advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7 nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1 μM was achieved with a UV fluence of 80 mJ/cm² and an initial H₂O₂ concentration of 882 μM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H₂O₂ concentration led to higher removal efficiency; however, the effect of HO scavenging by H₂O₂ became significant for high H₂O₂ concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6-117.8 mg CaCO₃/L) and NOM (as ∼2 to ∼9.5 mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1 μg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5 μg/L was spiked into those real water samples.     

Degradation mechanisms and kinetic studies for the treatment of X-ray contrast media compounds by advanced oxidation/reduction processes

The presence of iodinated X-ray contrast media compounds (ICM) in surface and ground waters has been reported. This is likely due to their biological inertness and incomplete removal in wastewater treatment processes. The present study reports partial degradation mechanisms based on elucidating the structures of major reaction by-products using γ-irradiation and LC-MS. Studies conducted at concentrations higher than observed in natural waters is necessary to elucidate the reaction by-product structures and to develop destruction mechanisms. To support these mechanistic studies, the bimolecular rate constants for the reaction of OH and e⁻_aq with one ionic ICM (diatrizoate), four non-ionic ICM (iohexol, iopromide, iopamidol, and iomeprol), and the several analogues of diatrizoate were determined. The absolute bimolecular reaction rate constants for diatrizoate, iohexol, iopromide, iopamidol, and iomeprol with OH were (9.58 ± 0.23)×10⁸, (3.20 ± 0.13)×10⁹, (3.34 ± 0.14)×10⁹, (3.42 ± 0.28)×10⁹, and (2.03 ± 0.13) × 10⁹ M⁻¹ s⁻¹, and with e⁻_aq were (2.13 ± 0.03)×10¹⁰, (3.35 ± 0.03)×10¹⁰, (3.25 ± 0.05)×10¹⁰, (3.37 ± 0.05)×10¹⁰, and (3.47 ± 0.02) × 10¹⁰ M⁻¹ s⁻¹, respectively. Transient spectra for the intermediates formed by the reaction of OH were also measured over the time period of 1-100 μs to better understand the stability of the radicals and for evaluation of reaction rate constants. Degradation efficiencies for the OH and e⁻_aq reactions with the five ICM were determined using steady-state γ-radiolysis. Collectively, these data will form the basis of kinetic models for application of advanced oxidation/reduction processes for treating water containing these compounds.     

Electrochemical degradation of β-blockers. Studies on single and multicomponent synthetic aqueous solutions

As far as we know, this is the first study reporting the electrochemical decontamination of solutions containing β-blockers, which are pharmaceutical pollutants with a high occurrence in natural waters. The oxidation ability of two pre-eminent, eco-friendly electrochemical advanced oxidation processes (EAOPs), namely anodic oxidation (AO) and electro-Fenton (EF), has been compared at lab-scale by carrying out bulk electrolyses at pH 3.0 at constant current using a carbon-felt cathode able to electrogenerate H₂O₂ in situ. The studies of single component aqueous solutions were focused on atenolol as a model β-blocker. The AO process was proven much more effective using a large surface area boron-doped diamond (BDD) anode than a Pt one, which was explained by the great amount of active hydroxyl radicals (BDD(OH)) and the minimization of their parasitic reactions. The EF process with a Pt anode and 0.2 mmol l⁻¹ Fe²⁺ showed even higher performance, with fast destruction of atenolol following pseudo-first order kinetics and fast mineralization because the oxidation process in the bulk allows overcoming the mass transport limitations. The time course of the concentration of the aromatic and short-chain carboxylic acid intermediates demonstrated the progressive detoxification of the solutions. Almost 100% of the initial N content was accumulated as NH₄⁺. Multicomponent solutions containing atenolol, metoprolol, and propranolol, which usually occur together in the aquatic environment, were treated by EF using the Pt/carbon felt cell. A high mineralization rate was observed up to the overall total organic carbon (TOC) removal, which allowed reducing the energy consumption. The absolute rate constant for the reaction of each β-blocker with OH was determined and the reactivity was found to increase in the order: atenolol (1.42 × 10⁹ l mol⁻¹ s⁻¹) < metoprolol (2.07 × 10⁹ l mol⁻¹ s⁻¹) < propranolol (3.36 × 10⁹ l mol⁻¹ s⁻¹).