Specific Ozone Dose Research Articles

Excessive Ozonation Stress Triggers Severe Membrane Biofilm Accumulation and Fouling.

The established benefits of ozone on microbial pathogen inactivation, natural organic matter degradation, and inorganic/organic contaminant oxidation have favored its application in drinking water treatment. However, viable bacteria are still present after the ozonation of raw water, bringing a potential risk to membrane filtration systems in terms of biofilm accumulation and fouling. In this study, we shed light on the role of the specific ozone dose (0.5 mg-O3/mg-C) in biofilm accumulation during long-term membrane ultrafiltration. Results demonstrated that ozonation transformed the molecular structure of influent dissolved organic matter (DOM), producing fractions that were highly bioavailable at a specific ozone dose of 0.5, which was inferred to be a turning point. With the increase of the specific ozone dose, the biofilm microbial consortium was substantially shifted, demonstrating a decrease in richness and diversity. Unexpectedly, the opportunistic pathogen Legionella was stimulated and occurred in approximately 40% relative abundance at the higher specific ozone dose of 1. Accordingly, the membrane filtration system with a specific ozone dose of 0.5 presented a lower biofilm thickness, a weaker fluorescence intensity, smaller concentrations of polysaccharides and proteins, and a lower Raman activity, leading to a lower hydraulic resistance, compared to that with a specific ozone dose of 1. Our findings highlight the interaction mechanism between molecular-level DOM composition, biofilm microbial consortium, and membrane filtration performance, which provides an in-depth understanding of the impact of ozonation on biofilm accumulation.

Comparison on removal performance of virus, antibiotic-resistant bacteria, cell-associated and cell-free antibiotic resistance genes, and indicator chemicals by ozone in the filtrated secondary effluent of a sewage treatment plant

Due to the widespread appearance of viruses, antibiotic-resistant bacteria (ARBs), and antibiotic resistance genes (ARGs) in the aquatic environment, more powerful oxidation processes such as ozonation are needed to enhance the efficiency of their inactivation and removal during wastewater treatment. However, information is lacking on the elimination rates of viruses, ARBs, cell-associated ARGs (ca-ARGs), and cell-free ARGs (cf-ARGs) during ozonation. This study examined the kinetics and dose-dependent inactivation of a virus (MS2 coliphage) and an ARB (Ampicillin-resistant [AmpR] E. coli) and the removal of ca- and cf-ARGs (plasmid-encoded blaTEM) by ozonation in a filtered secondary effluent (SE) of a municipal sewage treatment plant (STP). In addition, the ozonation kinetics of carbamazepine (CBZ) and metoprolol (MTP)—ubiquitous organic micropollutants with different removal rate constants—were also investigated in order to monitor their effectiveness as indicators for the abovementioned biological risk factors. Our results showed that ozonation was an efficient way to remove MS2, AmpRE. coli, ARGs, CBZ, and MTP. We investigated the kinetics of their inactivation/removal with respect to exposure in terms of CT (dissolved ozone concentration C and contact time T) value, and found their inactivation/removal constants were in the following order: MS2 (8.66 ×103 M−1s−1) ≈ AmpRE. coli (8.19 ×103 M−1s−1) > cf-ARG (3.95 ×103 M−1s−1) > CBZ (3.21 ×103 M−1s−1) > ca-ARG (2.48×103 M−1s−1) > MTP (8.35 ×102 M−1s−1). In terms of specific ozone dose, > 5-log inactivation of MS2 was observed at > 0.30 mg O3/mg DOC, while > 5-log inactivation of AmpRE. coli was confirmed at 1.61–2.35 mg O3/mg DOC. Moreover, there was almost no removal of ca-ARG when the specific ozone dose was < 0.68 mg O3/mg DOC. However, 2.86–3.42-log removal of ca-ARG was observed at 1.27–1.31 mg O3/mg DOC, while 1.14–1.36-log removal of cf-ARG was confirmed at 3.60–4.30 mg O3/mg DOC. As alternative indicators, > 4-log removal of CBZ was observed at > 1.00 mg O3/mg DOC, while > 2-log removal of MTP was confirmed at > 2.00 mg O3/mg DOC. Thus, it was observed that inactivation of E. coli needs a greater ozone dose to achieve the same level of inactivation of AmpRE. coli; for ARGs, cf-ARG can persist longer than ca-ARG if low dosages of ozone are applied in the filtrated SE, CBZ might act as an indicator with which to monitor the inactivation of viruses and ARBs, while MTP might act as an indicator with which to monitor removal of ARGs. Moreover, cf-ARG cannot be neglected even after ozonation due to the possibility that ca-ARGs can become cf-ARGs during ozonation and be discharged with the final effluent, posing a potential risk to the receiving environment.

Ozonation using a stainless-steel membrane contactor: Gas-liquid mass transfer and pharmaceuticals removal from secondary-treated municipal wastewater

A tubular porous stainless steel membrane contactor was characterized in terms of ozone-water mass transport, as well as its application in removing 23 pharmaceuticals (PhACs) detected in the secondary-treated municipal wastewater, under continuous mode operation. The volumetric mass transfer coefficient (KLa) was evaluated based on liquid flow rate, gas flow rate, and ozone gas concentration. The KLa values were substantially improved with an increment in liquid flow rate (1.6 times from 30 to 70 dm3 h−1) and gas flow rate (3.6 times from 0.30 to 0.85 Ndm3 min−1) due to the improved mixing in the gas-liquid interface. For the lowest liquid flow rate (30 dm3 h−1), the water phase boundary layer (82%) exhibited the major ozone transfer resistance, but it became almost comparable with membrane resistance for the highest liquid flow rate (70 dm3 h−1). Additionally, the influence of the specific ozone dose (0.39, 0.53, and 0.69 g O3 g DOC−1) and ozone inlet gas concentration (CO3,g,in = 27, 80, and 134 g Nm−3) were investigated in the elimination of 23 PhACs found in secondary-treated municipal wastewater. An ozone dose of 0.69 g O3 g DOC−1 and residence time of 60 s resulted in the removal of 12 out of the 23 compounds over 80%, while 17 compounds were abated above 60%. The elimination of PhACs was strongly correlated with kinetic reaction constants values with ozone and hydroxyl radicals (kO3 and kHO•), leading to a characteristic elimination pattern for each group of contaminants. This study demonstrates the high potential of membrane contactors as an appealing alternative for ozone-driven wastewater treatment.

Ecotoxicological mixture risk assessment of 35 pharmaceuticals in wastewater effluents following post-treatment with ozone and/or granulated activated carbon

Reducing the risk posed by mixtures of pharmaceuticals is a goal of current initiatives such as the European Green Deal to reduce anthropological environmental impacts. Wastewater effluent typically contains large numbers of active pharmaceutical ingredients (APIs). For some APIs, existing technology such as conventional activated sludge (CAS) wastewater treatment plants (WWTPs) have removal rates below 20 %, thus the WWTP discharges are adding to the toxic burden of receiving waters.We present an environmental risk assessment of mixtures of 35 APIs in effluent samples from 82 Northern European WWTPs using the concentration addition model, and identify the respective risk-driving APIs. This is then compared to a corresponding mixture risk assessment of effluent samples from the Danish Hillerød WWTP subjected to post-treatment with varying specific ozone doses (0.15–1.05 mgO3/mgDOC) and/or granulated activated carbon (GAC).All 82 WWTP effluent samples exceeded risk thresholds by at least a factor of 30, with a median RQSUM of 92.9, highlighting the need for effluent post-treatment and/or a substantial dilution in the recipient waters. Antibiotics, analgesics and anti-depressants were among the top risk drivers with 99 % of the average mixture risk attributable to azithromycin, diclofenac, venlafaxine, clarithromycin and mycophenolic acid. Effluent mixture risk was reduced by ozonation in a concentration-dependent manner, decreasing below threshold levels to a median RQSUM of 0.83 following treatment with 0.65 mgO3/mg DOC. Fresh GAC was also effective at reducing the mixture risk both alone and with ozone treatment, with median RQSUM of 0.04 and 0.07 respectively.To our knowledge, this is the first study to present a risk assessment of pharmaceutical mixtures in effluent comparing “conventional” WWTP processes with additional post-treatment with ozone and/or GAC for reducing the joint risks of pharmaceutical mixtures for recipient waters. We demonstrate the need for additional WWTP treatment technologies, and the efficacy of GAC and ozonation in decreasing the risk to the aquatic environment from pharmaceutical mixtures to below acceptable threshold limits.

Optimizing Ozone Disinfection in Water Reuse: Controlling Bromate Formation and Enhancing Trace Organic Contaminant Oxidation.

The use of ozone/biofiltration advanced treatment has become more prevalent in recent years, with many utilities seeking an alternative to membrane/RO based treatment for water reuse. Ensuring efficient pathogen reduction while controlling disinfection byproducts and maximizing oxidation of trace organic contaminants remains a major barrier to implementing ozone in reuse applications. Navigating these challenges is imperative in order to allow for the more widespread application of ozonation. Here, we demonstrate the effectiveness of ozone for virus, coliform bacteria, and spore forming bacteria inactivation in unfiltered secondary effluent, all the while controlling the disinfection byproduct bromate. A greater than 6-log reduction of both male specific and somatic coliphages was seen at specific ozone doses as low as 0.75 O3:TOC. This study compared monochloramine and hydrogen peroxide as chemical bromate control measures in high bromide water (Br- = 0.35 ± 0.07 mg/L). On average, monochloramine and hydrogen peroxide resulted in an 80% and 36% decrease of bromate formation, respectively. Neither bromate control method had any appreciable impact on virus or coliform bacteria disinfection by ozone; however, the use of hydrogen peroxide would require a non-Ct disinfection framework. Maintaining ozone residual was shown to be critical for achieving disinfection of more resilient microorganisms, such as spore forming bacteria. While extremely effective at controlling bromate, monochloramine was shown to inhibit TrOC oxidation, whereas hydrogen peroxide enhanced TrOC oxidation.

Removal of micropollutants and ecotoxicity during combined biological activated carbon and ozone (BO3) treatment

Ozonation is a viable option to improve the removal of micropollutants (MPs) in wastewater treatment plants (WWTPs). Nevertheless, the application of ozonation is hindered by its high energy requirements and by the uncertainties regarding the formation of toxic transformation products in the process. Energy requirements of ozonation can be reduced with a pre-ozone treatment, such as a biological activated carbon (BAC) filter, that removes part of the effluent organic matter before ozonation. This study investigated a combination of BAC filtration followed by ozonation (the BO3 process) to remove MPs at low ozone doses and low energy input, and focused on the formation of toxic organic and inorganic products during ozonation. Effluent from a WWTP was collected, spiked with MPs (approximately 1 µg/L) and treated with the BO3 process. Different flowrates (0.25–4 L/h) and specific ozone doses (0.2–0.6 g O3/g TOC) were tested and MPs, ecotoxicity and bromate were analyzed. For ecotoxicity assessment, three in vivo (daphnia, algae and bacteria) and six in vitro CALUX assays (Era, GR, PAH, P53, PR, andNrf2 CALUX) were used.Results show that the combination of BAC filtration and ozonation has higher MP removal and higher ecotoxicity removal than only BAC filtration and only ozonation. The in vivo assays show a low ecotoxicity in the initial WWTP effluent samples and no clear trend with increasing ozone doses, while most of the in vitro assays show a decrease in ecotoxicity with increasing ozone dose. This suggests that for the tested bioassays, feed water and ozone doses, the overall ecotoxicity of the formed transformation products during ozonation was lower than the overall ecotoxicity of the parent compounds. In the experiments with bromide spiking, relevant formation of bromate was observed above specific ozone doses of approximately 0.4 O3/g TOC and more bromate was formed for the samples with BAC pre-treatment. This indirectly indicates the effectivity of the pre-treatment in removing organic matter and making ozone more available to react with other compounds (such as MPs, but also bromide), but also underlines the importance of controlling the ozone dose to be below the threshold to avoid formation of bromate. It was concluded that treatment of the tested WWTP effluent in the BO3 process at a specific ozone dose of 0.2 g O3/g TOC, results in high MP removal at limited energy input while no increase in ecotoxicity, nor formation of bromate was observed under this condition. This indicates that the hybrid BO3 process can be implemented to remove MPs and improve the ecological quality of this WWTP effluent with a lower energy demand than conventional MP removal processes such as standalone ozonation.

Ozone membrane contactor for tertiary treatment of urban wastewater: Chemical, microbial and toxicological assessment

A membrane ozone contactor, operated under continuous mode, was applied to promote the tertiary treatment of urban wastewater (UWW), targeting the removal of contaminants of emerging concern (CECs), bacterial disinfection, and toxicity reduction. This system relies on the homogeneous radial distribution of ozone (O3) in the reaction zone by “titration” through a microfiltration borosilicate tubular membrane, while the UWW swirls around the membrane and drags the O3 microbubbles generated in the membrane shell-side. The membrane is coated with titanium dioxide (TiO2-P25) and radiation can be externally supplied via four UV lamps. The ozonation tests were carried out with secondary-treated UWW collected in different seasons (winter and summer) and spiked with a mix of 19 CECs (10 μg L−1 each). For an O3 dose of 18 g m−3, the best performance was obtained by increasing the O3 concentration (maximum [O3]G,inlet of 200 g Nm−3) and decreasing the gas flow rate (minimum QG of 0.15 Ndm3 min−1), providing the highest ozone transfer yield (88 %) and, thus higher specific ozone dose (g O3 per g dissolved organic carbon). Under these conditions, removals >80 % or concentrations below the limit of quantification were obtained for up to 13 of the 19 CECs and reductions up to 5 log units for total heterotrophs and below the limit of detection for enterobacteria and enterococci. Tests including a UVC dose of 0.10 kJ L−1 enhanced disinfection ability but had no impact on CECs oxidation. After ozonation, the abundance of antibiotic resistant bacteria was reduced but not eliminated, and microbial regrowth after 3-day storage was observed. No toxic effect was detected on zebrafish embryos using a dilution factor of 4 for the ozonized UWW and when granular activated carbon adsorption was subsequently applied the dilution factor decreased to 2.

Optimizing ozone dose and contact time for removal of antibiotic-resistant P. aeruginosa, A. baumannii, E. coli, and associated resistant genes in effluent of an activated sludge process in a municipal WWTP.

This study aimed to investigate the impact of ozonation on inactivation of antibiotic-resistant bacteria (ARB) including E. coli, P. aeruginosa, and A. baumannii, as well as on removal of 16S-rRNA gene and their associated antibiotic-resistant genes (ARGs) indigenously present in effluent of municipal wastewater treatment plant. The Chick-Watson model was used to describe bacterial inactivation rates at specific ozone doses. Maximum reduction of total cultivable A. baumannii, E. coli, and P. aeruginosa were found to be 7.6, 7.1, and 4.7 log, respectively, with the highest ozone dose of 0.48 gO3/gCOD at 12min contact time. According to the study results, complete inactivation of ARB and bacterial regrowth was not observed after 72h incubation. The culture methods overestimated the performance of disinfection processes and propidium monoazide combined with qPCR, and showed the presence of viable but non-culturable bacteria after ozonation. ARGs were more persistent to ozone than ARB. The results of this study highlighted the significance of specific ozone dose and contact time in ozonation process considering the bacterial species and associated ARGs as well as the wastewater physicochemical characteristics, in order to help diminish the entrance of the biological microcontaminants into the environment.

Formation of carbonyl compounds during ozonation of lake water and wastewater: Development of a non-target screening method and quantification of target compounds

Ozonation of natural waters is typically associated with the formation of carbonyl compounds (aldehydes, ketones and ketoacids), a main class of organic disinfection byproducts (DBPs). However, the detection of carbonyl compounds in water and wastewater is challenged by multiple difficulties inherent to their physicochemical properties. A non-target screening method involving the derivatisation of carbonyl compounds with p-toluenesulfonylhydrazine (TSH) followed by their analysis using liquid chromatography coupled to electrospray ionisation high-resolution mass spectrometry (LC-ESI-HRMS) and an advanced non-target screening and data processing workflow was developed. The workflow was applied to investigate the formation of carbonyl compounds during ozonation of different water types including lake water, aqueous solutions containing Suwannee River Fulvic acid (SRFA), and wastewater. A higher sensitivity for most target carbonyl compounds was achieved compared to previous derivatisation methods. Moreover, the method allowed the identification of known and unknown carbonyl compounds. 8 out of 17 target carbonyl compounds were consistently detected above limits of quantification (LOQs) in most ozonated samples. Generally, the concentrations of the 8 detected target compounds decreased in the order: formaldehyde > acetaldehyde > glyoxylic acid > pyruvic acid > glutaraldehyde > 2,3-butanedione > glyoxal > 1-acetyl-1-cyclohexene. The DOC concentration-normalised formation of carbonyl compounds during ozonation was higher in wastewater and SRFA-containing water than in lake water. The specific ozone doses and the type of the dissolved organic matter (DOM) played a predominant role for the extent of formation of carbonyl compounds. Five formation trends were distinguished for different carbonyl compounds. Some compounds were produced continuously upon ozonation even at high ozone doses, while others reached a maximum concentration at a certain ozone dose above which they decreased. Concentrations of target and peak areas of non-target carbonyl compounds during full-scale ozonation at a wastewater treatment plant showed an increase as a function of the specific ozone dose (sum of 8 target compounds ∼ 280 µg/L at 1 mgO3/mgC), followed by a significant decrease after biological sand filtration (> 64–94% abatement for the different compounds). This highlights the biodegradability of target and non-target carbonyl compounds and the importance of biological post-treatment.

Simulating the impact of ozonation on biodegradation characteristics of industrial wastewater concentrated with membrane filtration

The biodegradation of raw wastewater for an organized industrial zone has been studied by means of dedicated respirometric and analytical experiments. The experimental results indicated that the investigated industrial wastewater contains mainly the soluble (slowly) hydrolysable fraction of chemical oxygen demand (COD) (58 %) while readily biodegradable and soluble inert fractions were in the order of 19 % and 3 %, respectively. Full-scale dynamic modeling results successfully confirmed the validity of estimated COD fraction and biodegradation kinetics. End of pipe wastewater reuse potential studied with a pilot plant revealed that almost 100 % soluble inert organics could be concentrated in reverse osmosis (RO) reject. Expectedly, the concentration was far above the COD discharge limit of 200 mg/L. Subsequently, the application of specific ozone dose around 7 kg O3/(kg COD·hour) on RO concentrates was not sufficient to secure the discharge limit by itself. However, the ozone oxidation converted 85 % of inert COD into the (soluble) slowly biodegradable organic matter. The modeling studies also showed that biodegradable organic matter generated by ozonation has much lower degradation kinetics compared to mainstream sequencing batch reactor system.

Ozonation of lake water and wastewater: Identification of carbonous and nitrogenous carbonyl-containing oxidation byproducts by non-target screening

Ozonation of drinking water and wastewater is accompanied by the formation of disinfection byproducts (DBPs) such as low molecular weight aldehydes and ketones from the reactions of ozone with dissolved organic matter (DOM). By applying a recently developed non-target workflow, 178 carbonous and nitrogenous carbonyl compounds were detected during bench-scale ozonation of two lake waters and three secondary wastewater effluent samples and full-scale ozonation of secondary treated wastewater effluent. An overlapping subset of carbonyl compounds (20%) was detected in all water types. Moreover, wastewater effluents showed a significantly higher fraction of N-containing carbonyl compounds (30%) compared to lake water (17%). All carbonyl compounds can be classified in 5 main formation trends as a function of increasing specific ozone doses. Formation trends upon ozonation and comparison of results in presence and absence of the •OH radical scavenger DMSO in combination with kinetic and mechanistic information allowed to elucidate potential carbonyl structures. A link between the detected carbonyl compounds and their precursors was established by ozonating six model compounds (phenol, 4-ethylphenol, 4-methoxyphenol, sorbic acid, 3-buten-2-ol and acetylacetone). About one third of the detected carbonous carbonyl compounds detected in real waters was also detected by ozonating model compounds.Evaluation of the non-target analysis data revealed the identity of 15 carbonyl compounds, including hydroxylated aldehydes and ketones (e.g. hydroxyacetone, confidence level (CL) = 1), unsaturated dicarbonyls (e.g. acrolein, CL = 1; 2-butene-1,4-dial, CL = 1; 4-oxobut-2-enoic acid, CL = 2) and also a nitrogen-containing carbonyl compound (2-oxo-propanamide, CL =1).Overall, this study shows the formation of versatile carbonous and nitrogenous carbonyl compounds upon ozonation involving ozone and •OH reactions. Carbonyl compounds with unknown toxicity might be formed, and it could be demonstrated that acrolein, malondialdehyde, methyl glyoxal, 2-butene-1,4-dial and 4-oxo-pentenal are degraded during biological post-treatment.

Elimination of neonicotinoids by ozone-based advanced oxidation processes: Kinetics and performance in real water matrices

The Decision 2018/840 included some neonicotinoid insecticides (thiamethoxam (TMX), imidacloprid (ICP), clothianidin (CTD), thiacloprid (TCP), and acetamiprid (AMP)) within the watch list of substances for Union-wide monitoring in the field of water policy due to their potential risk to human health and the environment. In this work, the study of the elimination of these five neonicotinoids present in waters by ozone-based oxidation treatments has been carried out. While AMP and TCP presented very low rate constants with ozone and were hardly degraded, CTD (ozone rate constant of 116 M−1 s−1 at pH ≥ 7) and TMX (ozone rate constant of 22.7 M−1 s−1 for the studied pH range) were partially degraded by ozone. Furthermore, ICP ozonation showed a great pH dependence, with increasing ozone rate constant values from 2.7 M−1 s−1 at pH 5 to 160 M−1 s−1 at pH 9. In addition, rate constants for the reaction of neonicotinoids with hydroxyl radicals (•OH) were determined to be in the range (2.0–4.5)·109 M−1 s−1. The specific contribution of direct ozonation and radical pathways to the overall neonicotinoid degradation was evaluated, being the indirect oxidation with •OH dominant over direct ozone reactions. The influence of real water constituents such as dissolved organic matter (DOM) and bicarbonate, both acting as radical scavengers, on the ozonation process was negative. The ozone dose and the specific ozone dose required to remove neonicotinoids from real water matrices were higher than 5 mg/L and 1 mg O3 mg DOC-1, respectively, typically applied in water treatment. However, the application of the ozone-based advanced oxidation processes O3/H2O2 and O3/activated carbon provided an appreciable improvement in the elimination of neonicotinoids compared to ozone alone. Therefore, ozone-based advanced oxidation processes are needed to sufficiently abate neonicotinoids in contaminated waters.

Impact of ozone-biologically active filtration on the breakthrough of Perfluoroalkyl acids during granular activated carbon treatment of municipal wastewater effluent

The presence of perfluoroalkyl acids (PFAAs) in municipal wastewater has highlighted the need to develop PFAA treatment approaches for wastewater effluent and potable reuse applications. Ozone (O3) and biologically active filtration (BAF) were investigated as standalone and combined pretreatment processes to improve the performance of granular activated carbon (GAC) for PFAA removal from wastewater effluent. As individual processes, ozonation at all three investigated doses (0.35, 0.75, 1.0 mg O3/mg DOC) and BAF at both tested empty bed contact times (EBCT; 15 and 20 min) led to significant improvement in PFAA removal by subsequent GAC treatment. With respect to standalone ozonation, the specific O3 dose of 0.75 mg O3/mg DOC was proven to be the optimum operating condition as further increase of the specific ozone dose to 1.0 mg O3/mg DOC did not provide considerable additional improvement. Extending the EBCT during standalone BAF from 15 to 20 minutes significantly improved the efficacy of GAC for the removal of tested PFAAs. Pretreatment with O3-BAF (0.75 mg O3/mg DOC; 20 min EBCT) in tandem outperformed both standalone ozonation and BAF for the removal of PFAA by GAC. Characterization of effluent organic matter (EfOM) by size exclusion chromatography (SEC) and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR-MS) before and after pretreatments suggest that among multiple co-occurring phenomena, the shift towards smaller and more polar EfOM may have predominantly alleviated pore constriction/blockage without having adverse impact on direct site competition. This observation is supported by SEC and FT-ICR-MS results indicating reduced EfOM molecular size through O3 and BAF pretreatment as well as transition to more hydrophilic byproducts.

Elimination efficiency of synthetic musks during the treatment of drinking water with ozonation and UV-based advanced oxidation processes

This study investigated the reaction kinetics and elimination efficiency of eleven synthetic musks during ozonation and UV254nm-based, advanced oxidation processes. The synthetic musks containing olefin moieties with electron-donating alkyl substituents such as octahydro tetramethyl naphthalenyl ethanone (OTNE) and ambrettolide (AMBT) showed high reactivity toward ozone (k ≥ 3.7 × 105 M−1 s−1) and free available chlorine (FAC) (k = 9.2 – 88 M−1 s−1), while all other synthetic musks were less ozone reactive (k = 0.3 – 560 M−1 s−1) and FAC-refractory. All synthetic musks showed high •OH reactivity (k > 5 × 109 M−1 s−1), except musk ketone (MK) (k = 2.3 × 109 M−1 s−1). In concordance with the kinetic information, OTNE and AMBT were efficiently eliminated (>97%) in simulated ozone treatments of drinking water at a specific ozone dose of 0.5 gO3/gDOC. The elimination levels of the other synthetic musks were below 50% at 0.5 gO3/gDOC. The fluence-based UV photolysis rate constant of the synthetic musks was determined to be (0.2 – 2.7) × 10−3 cm2/mJ. The elimination levels of synthetic musks during UV alone treatment ranged from 7 to 81% at a UV fluence of 500 mJ/cm2. The addition of 10 mg/L H2O2 (UV/H2O2) significantly enhanced the elimination of most synthetic musks (achieving >90% elimination at 500 mJ/cm2), indicating that the •OH reaction was mainly responsible for their elimination. The addition of 10 mg/L FAC (UV/FAC) also significantly enhanced the elimination of olefinic and aromatic synthetic musks (>90%), for which the reaction with ClO• was mainly responsible. For MK and two alkyl synthetic musks, their elimination during UV/FAC treatment was still limited (28 – 64%) and was mainly achieved by UV photolysis or reaction with •OH. In summary, this study substantiates the chemical kinetics approach as a helpful tool for predicting or interpreting the elimination of micropollutants during oxidative water treatment.

Advanced wastewater treatment with ozonation and granular activated carbon filtration: Inactivation of antibiotic resistance targets in a long-term pilot study

The inactivation of antibiotic resistant bacteria (ARB) and genes (ARGs) in an advanced plant combining ozonation and granular activated carbon (GAC) filtration applied for effluent after conventional activated sludge treatment at a full-scale urban wastewater treatment plant was investigated for over 13 consecutive months. The nitrite compensated specific ozone dose ranged between 0.4 and 0.7 g O3/g DOC with short-time sampling campaigns (0.2–0.9 g O3/g DOC). Samples were analysed with culture-dependent methods for bacterial targets and with qPCR for genes. The log removal values were correlated with a decrease of the matrix UV absorption at 254 nm (ΔUV254) and indicated a range of ΔUV254 that corresponds to a sufficient membrane damage to affect DNA. For trimethoprim/sulfamethoxazole resistant E. coli, sul1, ermB and tetW, this phase was observed at ΔUV254 of ~30 % (~0.5 g O3/g DOC). For ampicillin resistant E. coli and blaTEM-1, it was observed around 35–40 % (~0.7 g O3/g DOC), which can be linked to mechanisms related to oxidative damages in bacteria resistant to bactericidal antibiotics. GAC treatment resulted in a further abatement for trimethoprim/sulfamethoxazole E. coli, sul1 and tetW, and in increase in absolute and relative abundance of ermB and blaTEM-1.

Decolorization and control of bromate formation in membrane ozonation of humic-rich groundwater

Membrane ozonation of bromide-containing, high-color natural organic matter (NOM) containing groundwater was performed using single-tube polydimethylsiloxane (PDMS) and multi-tube polytetrafluoroethylene (PTFE) membrane contactors, and compared to batch ozonation. For membrane ozonation, dissolved ozone concentration, water color (VIS436), ultraviolet light absorption (UV254) and bromate formation were correlated with ozone dose, ozone gas concentration, hydraulic retention time and Hatta number (Ha). NOM color removal of up to 45 % for the single-tube contactor and 17 % for the multi-tube contactor were achieved while containing bromate formation below 10 µg L−1. Higher color removal using higher ozone doses was associated with high bromate formation i.e. >>10 µg L−1. In membrane ozonation, low ozone gas concentrations, long hydraulic retention times and high Ha resulted in low dissolved ozone concentrations due to quenching of ozone by NOM. At specific ozone doses of < 0.5 mg O3/mg DOC and Ha > 1, single-tube ozonation resulted in comparable results to batch ozonation while bromate formation was higher in the single-tube contactor at specific ozone doses > 0.5 mg O3/mg DOC and Ha < 1. At comparable ozone doses and Ha, bromate formation in the multi-tube contactor was always higher compared to single-tube and batch ozonation. This could be associated with the uneven ozone distribution within the multi-tube contactor. Results show that ozone dose is the major driver for selectivity between bromate formation and NOM color removal in both membrane and batch ozonation. Bromate formation in membrane ozonation may be controlled by adjusting gas concentration, Ha and hydraulic retention time. Membrane module design and process parameters of membrane ozonation reactors significantly affect treatment performance and should be optimized for selective target compound removal over by-product formation.

Effect of ozonation on the biodegradability of urban wastewater treatment plant effluent

The present work aimed to study the effect of ozonation on the organic sum parameters linked to enhanced biodegradability. Laboratory experiments were conducted with the effluent of four Austrian urban wastewater treatment plants with low food to microorganism ratios and different matrix characteristics. Biochemical oxygen demand over 5 days (BOD5) was measured before ozonation and after application of different specific ozone doses (Dspec) (0.4, 0.6 and 0.8 g O3/g DOC). Other investigated organic parameters comprised chemical oxygen demand (COD), dissolved organic carbon (DOC), UV absorption at 254 nm (UV254), which are parameters that are applied in routine wastewater analysis. Carbamazepine and benzotriazole were measured as reference micropollutants. The results showed a dose-dependent increase in biological activity after ozonation; this increase was linked to the enhanced biodegradability of substances that are recalcitrant to biodegradation in conventional activated sludge treatment. The highest relative change was determined for BOD5, which already occurred between 0 and 0.4 g O3/g DOC for all samples. Increasing the Dspec to 0.6 and 0.8 g O3/g DOC resulted in a less pronounced increase. DOC was not substantially decreased after ozonation, which was consistent with a low reported degree of mineralization, while partial oxidation led to a quantifiable decrease in COD (7 to 17%). Delta UV254 and the decline in specific UV absorption after ozonation clearly correlated with Dspec. In contrast, for COD and biodegradable DOC (BDOC), a clear dose-response pattern was identified only after exposure to BOD5 measurement. Indications for improved biodegradability were further supported by the rise in the BOD5/COD ratio. The results indicated that subsequent biological processes have a higher degradation potential after ozonation. The further reduction in biodegradable organic carbon emission by the combination of ozonation and biological post treatment represents another step towards sustainable water resource management in addition to micropollutant abatement.

Reaction kinetics and degradation efficiency of halogenated methylparabens during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent

This study investigated the reaction kinetics and degradation efficiency of methylparaben and its halogenated products (Cl-, Br-, Cl,Cl-, Br,Cl-, and Br,Br-methylparabens) during ozonation and UV254/H2O2 treatment. Second-order rate constants for reactions of the parabens with ozone and •OH were kO3 = 107 – 108 M−1 s−1 and k•OH = (2.3 – 4.3)× 109 M−1 s−1 at pH 7. Species-specific kO3 values of the protonated and deprotonated parabens were closely related to phenol ring substituent effects via quantitative structure-activity relationships with other substituted phenols. The UV photolysis rate of the parabens [kUV = (2.4 − 7.2)× 10−4 cm2 mJ−1] depended on the halogenation state of the paraben and solution pH, from which species-specific quantum yields were also determined. In simulated treatments of drinking water and wastewater effluent, the parabens were efficiently eliminated during ozonation, requiring a specific ozone dose of > 0.26 gO3/gDOC for > 97% degradation. During UV/H2O2 treatment with 10 mg L−1 H2O2, the degradation levels were > 90% at a UV fluence of 2000 mJ cm−2, except for Cl,Cl-methylparaben. Kinetic models based on the obtained reaction kinetic parameters could successfully predict the degradation levels of the parabens. Overall, ozonation and UV/H2O2 were effective in controlling parabens and their halogenated products during advanced water treatment.

Reactions of amines with ozone and chlorine: Two novel oxidative methods to evaluate the N-DBP formation potential from dissolved organic nitrogen

The composition of oxidant-reactive dissolved organic nitrogen (DON) is poorly characterized, although its ozonation is likely to form a great variety of disinfection by-products containing a nitrogen-oxygen bond (N-DBPs). In this study, two chemical oxidation procedures were developed: continuous ozonation at pH 7.0 and free available chlorine (FAC) titrations at pH 9.2. The formation of two oxidation products (nitrate (NO3−) and chloramines, respectively) was used to quantify and characterize oxidant-reactive nitrogenous moieties in DON. In addition, batch experiments were conducted to study the NO3− yields of 30 selected nitrogenous model compounds upon ozonation. The NO3− yields of 12 primary and secondary amines were highly variable (17–100%, specific ozone dose of 20 molO3/molN), 7 amino acids had high NO3− yields (≥90%), and tertiary amines as well as pyrrole, acetamide and urea had low NO3− yields (≤15%). The mechanisms of NO3− formation were further examined with benzylamine and N-methylbenzylamine as model compounds. Our results show that nitroalkanes are the last intermediate products before the formation of NO3−, both for primary and secondary amines. The presence of an electron-withdrawing group in the vicinity of the N-atom facilitates the formation of NO3− from nitroalkanes. Therefore, the formation of NO3− is attributed to amino acids and activated primary and secondary amines. In contrast, all primary and secondary amines were transformed to chloramines upon chlorination, which was determined by a novel oxidative titration with chlorine. To further support the selectivity of this assay, it was demonstrated by derivatization of amine moieties that chloramine formation could be inhibited. 13–45% of the DON of 4 dissolved organic matter isolates and 2 wastewater effluents formed NO3− and 0–39% formed chloramines, indicating that the potential for N-DBP formation is high (µMN/mgC-level). From differences in the formation of NO3− and chloramines the nature of the precursors can be hypothesized (e.g., activated or non-activated primary and secondary amines, partially oxidized nitrogenous compounds). This study highlights the capacity of two novel methods to characterize the oxidant-reactive DON fraction. Our results suggest that this fraction is significant and could form a variety of potentially toxic N-DBPs.

Application of UV absorbance and electron-donating capacity as surrogates for micropollutant abatement during full-scale ozonation of secondary-treated wastewater

Ozonation of secondary-treated wastewater for the abatement of micropollutants requires a reliable control of ozone doses. Changes in the UV absorbance of dissolved organic matter (DOM) during ozonation allow to estimate micropollutant abatement on-line and were therefore identified as feed-back control parameter. In this study, the suitability of the electron-donating capacity (EDC) as an additional surrogate parameter which is independent of optical DOM properties was evaluated during full-scale ozonation. For this purpose, a recently developed EDC analyzer was enhanced to enable continuous on-line EDC and UV absorbance measurements. During a multi-week monitoring campaign at the wastewater treatment plant of Zurich, Switzerland, specific ozone doses were varied from 0.13 to 0.91 mgO3⋅mgDOC−1 and selected micropollutants with different ozone reactivities were analyzed by LC-MS in conjunction with bromate analysis by IC-MS. In agreement with previous laboratory studies, the relative residual UV absorbance and EDC both decreased exponentially as a function of the specific ozone dose and, in comparison to the residual UV absorbance, residual EDC values showed a more pronounced decrease at low specific ozone doses ≤0.34 mgO3⋅mgDOC−1. Logistic regression models allowed to estimate relative residual micropollutant concentrations in the ozonation effluent using either the residual UV absorbance or EDC as explanatory variable. Averaging those models along the explanatory variables allowed to estimate target values in relative residual UV absorbances and EDC for specific micropollutant abatement targets. In addition, both parameters allowed to identify conditions with elevated conversions of bromide to bromate. Taken together, these findings show that the integration of relative residual EDC values as a second control parameter can improve existing absorbance-based ozonation control systems to meet micropollutant abatement targets, particularly for treatment systems where low ozone doses are applied.