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.     

Measurement of the initial phase of ozone decomposition in water and wastewater by means of a continuous quench-flow system: application to disinfection and pharmaceutical oxidation

Due to a lack of adequate experimental techniques, the kinetics of the first 20s of ozone decomposition in natural water and wastewater is still poorly understood. Introducing a continuous quench-flow system (CQFS), measurements starting 350 ms after ozone addition are presented for the first time. Very high HO. to O3 exposures ratios (Rct=integralHO.dt/integralO3dt) reveal that the first 20s of ozonation present oxidation conditions that are similar to ozone-based advanced oxidation processes (AOP). The oxidation of carbamazepine could be accurately modeled using O3 and HO. exposures measured with CQFS during wastewater ozonation. These results demonstrate the applicability of bench scale determined second-order rate constants for wastewater ozonation. Important degrees of pharmaceutical oxidation and microbial inactivation are predicted, indicating that a significant oxidation potential is available during wastewater ozonation, even when ozone is entirely decomposed in the first 20s.     

Formation of nitrosodimethylamine (NDMA) during chlorine disinfection of wastewater effluents prior to use in irrigation systems

The probable human carcinogen nitrosodimethylamine (NDMA) is produced when wastewater effluent is disinfected with chlorine. In systems where wastewater effluent is used for landscape or crop irrigation, relatively high chlorine doses (i.e., up to 2,000,mg-min/L) are often used to ensure adequate disinfection and to minimize biofouling in the irrigation system. To assess the formation of NDMA in such systems, samples were collected from several locations in full-scale wastewater treatment systems and their associated irrigation systems. Up to 460 ng/L of NDMA was produced in full-scale systems in which chloramines were formed when wastewater effluent was disinfected with chlorine in the presence of ammonia. Less than 20 ng/L of NDMA was produced in systems that used free chlorine (i.e., HOCl/OCl(-)) for disinfection in the absence of ammonia. The production of NDMA in ammonia-containing systems was correlated with the concentration of NDMA precursors in the wastewater effluent and the overall dose of chlorine applied. Much of the NDMA formation occurred in chlorine contact basins or in storage basins where water that contained chloramines was held after disinfection. When landscape or crop irrigation is practiced with ammonia-containing wastewater effluent, NDMA production can be controlled by use of lower chlorine doses or by application of alternative disinfectants.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Removal of disinfection by-product precursors with ozone-UV advanced oxidation process

The efficacy of using ozone (O3), ultraviolet irradiation (UV) and the combined O3-UV advanced oxidation process (AOP) to remove 2 classes of disinfection by-product (DBP) precursors from raw surface water samples have been evaluated and compared. In particular, trihalomethane and haloacetic acids formation potentials were measured. Laboratory batch scale experiments were carried out as a function of ozone and UV dosage in order to study the removal kinetics. It is concluded that the combined O3-UV AOP is more effective than either the ozone or UV treatment alone. Ozone-UV AOP is capable of mineralizing up to 50% of the total organic carbon from the raw source water at an ozone dose of 0.62+/-0.019 mg O3/mL and a UV dose of 1.61 W s/cm2. In addition, O3-UV AOP can reduce trihalomethane formation potential by roughly 80% and haloacetic acids formation potential by roughly 70% at the same ozone and UV dosage.     

Advanced oxidation effect of ozonation combined with electrolysis

The advanced oxidation effect of ozonation combined with electrolysis (electrolysis-ozonation) was discussed through the treatment of 4-chlorobenzoic acid (4-CBA) as a hydroxyl radical probe. The mechanism of hydroxyl radical production by electrolysis-ozonation process was also estimated with a mathematical model. The experimental results revealed that the electrolysis-ozonation process had a synergistic effect on the degradation of 4-CBA. The advanced oxidation effect of electrolysis-ozonation was inferred from standard potentials of relevant electrochemical reactions and mathematical model analysis to be mainly attributed to ()O(3)(-) promotion of O(3) at the cathodes. An increase in electric current improved the degradation rate of 4-CBA. However, the pseudo-first order degradation rate constant reached a plateau at high electric current densities, as ()O(3)(-) promotion of O(3) at the cathodes was regulated by O(3) transport process from the bulk to the cathodes in the range exceeding an electric current density of 10 Am(-2). Accordingly, the balance of O(3) transport flux and electric current is important for the efficient operation of the electrolysis-ozonation reactor.     

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.     

Oxidation of organics in retentates from reverse osmosis wastewater reuse facilities

The use of membrane processes for wastewater treatment and reuse is rapidly expanding. Organic, inorganic, and biological constituents are effectively removed by reverse osmosis (RO) membrane processes, but concentrate in membrane retentates Disposal of membrane concentrates is a growing concern. Applying advanced oxidation processes (AOPs) to RO retentate is logical because extensive treatment and energy inputs were expended to concentrate the organics, and it is cheaper to treat smaller flowstreams. AOPs (e.g., UV irradiation in the presence of titanium dioxide; UV/TiO₂) can remove a high percentage of organic matter from RO retentates. The combination of AOPs and a simple biological system (e.g., sand filter) can remove higher levels of organic matter at lower UV dosages because AOPs produce biologically degradable material (e.g., organic acids) that have low hydroxyl radical rate constants, meaning that their oxidation, rather than that of the primary organic matter in the RO retentate, dictates the required UV energy inputs. At the highest applied UV dose (10 kWh m⁻3), the dissolved organic carbon (DOC) in the RO retentate decreased from ∼40 to 8 mg L⁻1, of which approximately 6 mg L⁻1 were readily biologically degradable. Therefore, after combined UV treatment and biodegradation, the final DOC concentration was 2 mg L⁻1, representing a 91% removal. These results suggest that UV/TiO₂ plus biodegradation of RO retentates is feasible and would significantly reduce the organic pollutant loading into the environment from wastewater reuse facilities.     

Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.     

Removal of refractory compounds from stabilized landfill leachate using an integrated H2O2 oxidation and granular activated carbon (GAC) adsorption treatment

This study investigated the treatment performances of H₂O₂ oxidation alone and its combination with granular activated carbon (GAC) adsorption for raw leachate from the NENT landfill (Hong Kong) with a very low biodegradability ratio (BOD₅/COD) of 0.08. The COD removal of refractory compounds (as indicated by COD values) by the integrated H₂O₂ and GAC treatment was evaluated, optimized and compared to that by H₂O₂ treatment alone with respect to dose, contact time, pH, and biodegradability ratio. At an initial COD concentration of 8000 mg/L and NH₃-N of 2595 mg/L, the integrated treatment has substantially achieved a higher removal (COD: 82%; NH₃-N: 59%) than the H₂O₂ oxidation alone (COD: 33%; NH₃-N: 4.9%) and GAC adsorption alone (COD: 58%) at optimized experimental conditions (p ≤ 0.05; t-test). The addition of an Fe(II) dose at 1.8 g/L further improved the removal of refractory compounds by the integrated treatment from 82% to 89%. Although the integrated H₂O₂ oxidation and GAC adsorption could treat leachate of varying strengths, treated effluents were unable to meet the local COD limit of less than 200 mg/L and the NH₃-N of lower than 5 mg/L. However, the integrated treatment significantly improved the biodegradability ratio of the treated leachate by 350% from 0.08 to 0.36, enabling the application of subsequent biological treatments for complementing the degradation of target compounds in the leachate prior to their discharge.     

Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes

The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone ( [Formula: see text] =3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.     

Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254 + 185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 × 10⁻³ m² J⁻¹ for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 × 10⁻⁴ m² J⁻¹ for geosmin and 2.5 × 10⁻⁴ m² J⁻¹ for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L⁻¹ nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.     

An evaluation of a pilot-scale nonthermal plasma advanced oxidation process for trace organic compound degradation

This study evaluated a pilot-scale nonthermal plasma (NTP) advanced oxidation process (AOP) for the degradation of trace organic compounds such as pharmaceuticals and potential endocrine disrupting compounds (EDCs). The degradation of seven indicator compounds was monitored in tertiary-treated wastewater and spiked surface water to evaluate the effects of differing water qualities on process efficiency. The tests were also conducted in batch and single-pass modes to examine contaminant degradation rates and the remediation capabilities of the technology, respectively. Values for electrical energy per order (EEO) of magnitude degradation ranged from <0.3 kWh/m³-log for easily degraded compounds (e.g., carbamazepine) in surface water to 14 kWh/m³-log for more recalcitrant compounds (e.g., meprobamate) in wastewater. Changes in the bulk organic matter based on UV₂₅₄ absorbance and excitation-emission matrices (EEM) were also monitored and correlated to contaminant degradation. These results indicate that NTP may be a viable alternative to more common AOPs due to its comparable energy requirements for contaminant degradation and its ability to operate without any additional feed chemicals.     

Paracetamol oxidation from aqueous solutions by means of ozonation and H2O2/UV system

Paracetamol oxidation from aqueous solutions is studied by means of ozonation and H(2)O(2) photolysis. Both oxidative systems are able to destroy the aromatic ring of the substrate with a partial conversion of the initial carbon content into carbon dioxide. For the adopted experimental conditions mineralization degrees up to 30% and 40% are observed with ozonation and H(2)O(2) photolysis, respectively. Main reaction intermediates and products are identified for both systems by HPLC and GC-MS analyses and a kinetic characterization is achieved.     

Degradation of pharmaceutical compound pentoxifylline in water by non-thermal plasma treatment

The decomposition of a model pharmaceutical compound, pentoxifylline, in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration, operated in pulsed regime, at atmospheric pressure and room temperature. The solution was made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. Oxygen was introduced with a flow rate of 600 sccm. After 60 min plasma treatment 92.5% removal of pentoxifylline was achieved and the corresponding decomposition yield was 16 g/kWh. It was found that pentoxifylline degradation depended on the initial concentration of the compound, being faster for lower concentrations. Faster decomposition of pentoxifylline could be also achieved by increasing the pulse repetition rate, and implicitly the power introduced in the discharge, however, this had little effect on the decomposition yield. The degradation products were investigated by liquid chromatography-mass spectrometry technique (LC-MS). The evolution of the intermediates during plasma treatment showed a fast increase in the first 30 min, followed by a slower decrease, so that these products are almost completely removed after 120 min treatment time.     

Comparison of advanced oxidation processes for the removal of natural organic matter

This study examined the impact of UV, ozone (O₃), advanced oxidation processes (AOPs) including O₃/UV, H₂O₂/UV H₂O₂/O₃ in the change of molecular weight distribution (MWD) and disinfection by-product formation potential (DBPFP). Bench-scale experiments were conducted with surface river water and changes in the UV absorbance at 254 nm (UV₂₅₄), total organic carbon (TOC), trihalomethane and haloacetic acid formation potential (THMFP, HAAFP) and MWD of the raw and oxidized water were analyzed to evaluate treatment performance. Combination of O₃ and UV with H₂O₂ was found to result in more TOC and UV₂₅₄ reduction than the individual processes. The O₃/UV process was found to be the most effective AOP for NOM reduction, with TOC and UV₂₅₄ reduced by 31 and 88%, respectively. Application of O₃/UV and H₂O₂/UV treatments to the source waters organics with 190-1500 Da molecular weight resulted in the near complete alteration of the molecular weight of NOM from >900 Da to <300 Da H₂O₂/UV was found to be the most effective treatment for the reduction of THM and HAA formation under uniform formation conditions. These results could hold particular significance for drinking water utilities with low alkalinity source waters that are investigating AOPs, as there are limited published studies that have evaluated the treatment efficacy of five different oxidation processes in parallel.     

Characterization of effluent water qualities from satellite membrane bioreactor facilities

Membrane bioreactors (MBRs) are often a preferred treatment technology for satellite water recycling facilities since they produce consistent effluent water quality with a small footprint and require little or no supervision. While the water quality produced from centralized MBRs has been widely reported, there is no study in the literature addressing the effluent quality from a broad range of satellite facilities. Thus, a study was conducted to characterize effluent water qualities produced by satellite MBRs with respect to organic, inorganic, physical and microbial parameters. Results from sampling 38 satellite MBR facilities across the U.S. demonstrated that 90% of these facilities produced nitrified (NH₄-N <0.4 mg/L-N) effluents that have low organic carbon (TOC <8.1 mg/L), turbidities of <0.7 NTU, total coliform bacterial concentrations <100 CFU/100 mL and indigenous MS-2 bacteriophage concentrations <21 PFU/100 mL. Multiple sampling events from selected satellite facilities demonstrated process capability to consistently produce effluent with low concentrations of ammonia, TOC and turbidity. UV-254 transmittance values varied substantially during multiple sampling events indicating a need for attention in designing downstream UV disinfection systems. Although enteroviruses, rotaviruses and hepatitis A viruses (HAV) were absent in all samples, adenoviruses were detected in effluents of all nine MBR facilities sampled. The presence of Giardia cysts in filtrate samples of two of nine MBR facilities sampled demonstrated the need for an appropriate disinfection process at these facilities.     

Pilot-scale evaluation of ozone and biological activated carbon for trace organic contaminant mitigation and disinfection

In an effort to validate the use of ozone for contaminant oxidation and disinfection in water reclamation, extensive pilot testing was performed with ozone/H₂O₂ and biological activated carbon (BAC) at the Reno-Stead Water Reclamation Facility in Reno, Nevada. Three sets of samples were collected over a five-month period of continuous operation, and these samples were analyzed for a suite of trace organic contaminants (TOrCs), total estrogenicity, and several microbial surrogates, including the bacteriophage MS2, total and fecal coliforms, and Bacillus spores. Based on the high degree of microbial inactivation and contaminant destruction, this treatment train appears to be a viable alternative to the standard indirect potable reuse (IPR) configuration (i.e., membrane filtration, reverse osmosis, UV/H₂O₂, and aquifer injection), particularly for inland applications where brine disposal is an issue. Several issues, including regrowth of coliform bacteria in the BAC process, must be addressed prior to full-scale implementation.     

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV₂₅₄ absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications.     

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water

A photocatalytic reactor membrane pilot system, employing UV/TiO₂ photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m³). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H₂O₂ mode (UV/H₂O₂) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H₂O₂ mode for the conditions tested.