In advanced oxidation processes, the application of ozonation has been immensely used in recent years for the treatment of effluent water from pharmaceutical, textile and chemical industries. In this study, procian blue, a major and vastly used reactive dye in the textile industry was chosen for ozonation. This work investigated the effect of ozonation for the treatment of synthetic textile effluent water. The change of pH values of dye solutions from 2-12 had moderate effect on dye removal. The degradation rate was faster during the initial period of ozonation and reached highest dye removal around 90 minutes. The highest 87% removal of dye was observed for the case of 60 mg/L dye solution at pH 12. At higher pH, the dye degradation increased as the rate of formation of hydroxyl radical increased with pH. Factors influencing on dye degradation like concentration of dye, time of ozonation, and addition of H2O2 with ozone (combined treatment) were also evaluated. The combined treatment (5 g/L of hydrogen peroxide) increased the degradation of dye to 92% as compared to 85% for pure ozonation process of 60 mg/L dye solution of initial pH 10. The procian blue dye degradation followed pseudo-first order kinetics with a value of rate constant 2.48×10-2 /min.

We investigated the fates of seven neonicotinoids (NNIs) in full-scale drinking water treatment plants and assessed human exposure to NNIs through consuming drinking water. The total NNI concentrations in raw water and treated water samples from the drinking water treatment plants were 20.4–166 ng/L (median 118 ng/L) and 1.11–94.7 ng/L (median 20.4 ng/L), respectively. The dinotefuran (DIN) concentrations in raw water collected in different seasons were different, and the highest DIN concentration was found in summer. The drinking water treatment processes removed >91% of the NNIs except DIN and thiamethoxam (THIAM), for which the mean removal rates were 70% and 74%, respectively. The removal rates for all of the NNIs were higher for the granular activated carbon filtration process (mean 83.5%) than the other drinking water treatment plant processes (coagulation/sedimentation 22.3%, ozonation 29.2%). However, the removal rates in the granular activated carbon process were lower for DIN and THIAM (61.0% and 59.2%, respectively) than the other NNIs. Significant correlations were found between the NNI removal rates and physicochemical properties (solubility in water and log (octanol–water partition coefficient)). The estimated mean human exposure to NNIs in drinking water was 0.528 ng/(kg body weight d).

Rising tropospheric ozone concentrations in Asia affect the yield and quality of rice. This study investigated ozone-induced changes in rice grain quality in contrasting rice genotypes, and explored the associated physiological processes during the reproductive growth phase. The ozone sensitive variety Nipponbare and a breeding line (L81) containing two tolerance QTLs in Nipponbare background were exposed to 100 ppb ozone (8 h per day) or control conditions throughout their growth. Ozone affected grain chalkiness and protein concentration and composition. The percentage of chalky grains was significantly increased in Nipponbare but not in L81. Physiological measurements suggested that grain chalkiness was associated with a drop in foliar carbohydrate and nitrogen levels during grain filling, which was less pronounced in the tolerant L81. Grain total protein concentration was significantly increased in the ozone treatment, although the albumin fraction (water soluble protein) decreased. The increase in protein was more pronounced in L81, due to increases in the glutelin fraction in this genotype. Amino acids responded differently to the ozone treatment. Three essential amino acids (leucine, methionine and threonine) showed significant increases, while seven showed significant treatment by genotype interactions, mostly due to more positive responses in L81. The trend of increased grain protein was in contrast to foliar nitrogen levels, which were negatively affected by ozone. A negative correlation between grain protein and foliar nitrogen in ozone stress indicated that higher grain protein cannot be explained by a concentration effect in all tissues due to lower biomass production. Rather, ozone exposure affected the nitrogen distribution, as indicated by altered foliar activity of the enzymes involved in nitrogen metabolism, such as glutamine synthetase and glutamine-2-oxoglutarate aminotransferase. Our results demonstrate differential responses of grain quality to ozone due to the presence of tolerance QTL, and partly explain the underlying physiological processes.

Synergistic effects of ozone (O₃) and peroxymonosulfate (PMS, HSO₅⁻) for isothiazolinone biocides degradation was studied. The synergistic ozonation process (O₃/PMS) increased the efficiency of methyl-isothiazolinone (MIT) and chloro-methyl-isothiazolinone (CMIT) degradation to 91.0% and 81.8%, respectively, within 90 s at pH 7.0. This is 30.6% and 62.5% higher than the corresponding ozonation efficiency, respectively. Total radical formation value (Rcₜ,R) for the O₃/PMS process was 24.6 times that of ozonation alone. Calculated second-order rate constants for the reactions between isothiazolinone biocides and ▪ (kSO₄₋,MIT and kSO₄₋,CMIT) were 8.15 × 10⁹ and 4.49 × 10⁹ M⁻¹ s⁻¹, respectively. Relative contributions of O₃, hydroxyl radical (OH) and ▪ oxidation to MIT and CMIT removal were estimated, which were 15%, 45%, and 40% for O₃, OH and ▪ oxidation to MIT, and 1%, 67%, and 32% for O₃, OH and ▪ oxidation to CMIT at pH 7.0, respectively. Factors influencing the O₃/PMS process, namely the solution pH, chloride ions (Cl⁻), and bicarbonate (HCO₃⁻), were evaluated. Increasing the solution pH markedly accelerated O₃ decay and OH and ▪ formation, thus weakening the relative contribution of O₃ oxidation while enhancing that of OH and ▪. Cl⁻ had a negligible effect on MIT and CMIT degradation. Under the dual effect of bicarbonate (HCO₃⁻) as inhibitor and promoter, low concentrations (1–2 mM) of bicarbonate weakly promoted MIT and CMIT degradation, while high concentrations (10–20 mM) induced strong inhibition. Lastly, oxidation performance of O₃ and O₃/PMS processes for MIT and CMIT degradation in different water matrices was compared.

The search for optimal catalysts to improve the working efficiency of ozonation has always been an important issue in the research field of advanced oxidation processes. In this study, a novel catalyst, ferrosilicon, was selected as the catalyst in heterogeneous catalytic ozonation to degrade ibuprofen (IBP) in water and treat real pharmaceutical wastewater. During the procedure, 45#ferrosilicon exhibited the best catalytic activity. Under the optimized experimental conditions, the IBP removal reached 75%, which was a great improvement compared to the 37% removal by ozone alone. The 45#-ferrosilicon-catalysed ozonation also achieved 68% TOC removal for real pharmaceutical wastewater, which was 31% higher than that by ozone alone. The degradation pathway of IBP was proposed using GC/MS. The EPR test proved that the main active species in the system were free active radicals •OH, and the measured accumulative •OH amount was 102 μmol. The characterization results show that the nascent metallic oxides, hydroxides, and hydroxyoxides on the ferrosilicon surface facilitated the decomposition of ozone molecules and generation of free active radicals. The removal of target organic contaminants in the water was mainly attributed to the oxidization of these highly active species.

To date, micropollutants from anthropogenic sources cannot be completely removed from effluents of wastewater treatment plants and therefore enter freshwater systems, where they may impose adverse effects on aquatic organisms, for example, on fish. Advanced treatment such as ozonation aims to reduce micropollutants in wastewater effluents and, thus, to mitigate adverse effects on the environment. To investigate the impact and efficiency of ozonation, four different water types were tested: ozonated wastewater (before and after biological treatment), conventionally-treated wastewater, and water from a river (River Ruhr, Germany) upstream of the wastewater treatment plant effluent. Zebrafish (Danio rerio) embryos were used to study lethal and sublethal effects in a modified fish early life-stage test. Mortality occurred during exposure in the water samples from the wastewater treatment plant and the river in the first 24 h post-fertilization, ranging from 12% (conventional wastewater) to 40% (river water). Regarding sublethal endpoints, effects compared to the negative control resulted in significantly higher heart rates (ozonated wastewater), and significantly reduced swimming activity (highly significant in ozonated wastewater and ozone reactor water, significant in only the last time interval in river water). Moreover, the respiration rates were highly increased in both ozonated wastewater samples in comparison to the negative control. Significant differences between the ozonated wastewater samples occurred in the embryonic behavior and heart rates, emphasizing the importance of subsequent biological treatment of the ozonated wastewater. Only the conventionally-treated wastewater sample did not elicit negative responses in zebrafish, indicating that the discharge of conventional wastewater poses no greater risk to embryonic and larval zebrafish than water from the river Ruhr itself. The sublethal endpoints embryonic- and larval behavior, heart rates, and respiration were found to be the most sensitive endpoints in this fish early life-stage test and can add valuable information on the toxicity of environmental samples.

Four phenylurea herbicides (PUHs) were assessed for degradation and transformation into N-nitrosodimethylamine (NDMA) under three oxidation conditions (chlorine (Cl₂), chlorine dioxide (ClO₂), and ozone (O₃)) from an aqueous solution. Removal ratios correlated with the numbers of halogen elements contained in PUHs (isoproturon ₍₀₎ > chlorotoluron ₍₁ Cₗ₎ > diuron ₍₂ Cₗ₎ > fluometuron ₍₃ F₎), and the degradation efficiencies of oxidants from fastest to slowest were: O₃, ClO₂, and Cl₂. NDMA can be generated directly from the ozonation of PUHs. Further, compared with chloramination alone, ozonation prominently promoted NDMA formation potential (NDMA-FP) during post-chloramination, and NDMA-FPs increased approximately 23–68 times than those during ozonation only at 2.5 mg/L O₃ over 10 min; molar yields of NDMA from highest to lowest were 11.1% (isoproturon), 1.17% (chlorotoluron), 1.0% (diuron), and 0.73% (fluometuron). The PUH degradation kinetics data during ozonation agreed with the pseudo-first-order model. The rate constant kₒbₛ were 0.31 × 10⁻³–19.8 × 10⁻³ s⁻¹. The kₒbₛ and removal ratios of PUHs during ozonation partially scaled with the mass, LogKₒw, and Henry’s constants of PUHs. Comparisons of measured NDMA-FPs with calculated NDMA-FPs from residual PUH after oxidation showed that the intermediates produced during ozonation facilitated NDMA-FPs; this contribution was also observed for chlorotoluron and isoproturon during ClO₂ oxidation. Examination of reaction mechanisms revealed that tertiary amine ozonation, N-dealkylation, hydroxylation, the cleavage of N–C bonds, ammonification, and nitrification occurred during the ozonation of PUHs, and the dimethylamine (DMA) functional groups could be decomposed directly and transformed into NDMA via the formation of the intermediate unsymmetrical dimethylhydrazine. NDMA is also formed from the reaction between DMA and phenylamino-compounds. Clarifying primary degradation products of PUHs and transformation pathways of NDMA during oxidation processes is useful to optimize treatment processes for water supplies.

Effluent is often treated with ozone before being discharged into a natural water environment. This process will change the interaction between effluent organic matter and pollutants in aquatic environment. The impact of ozonation on complexation between dissolved organic matter in such wastewater and sulfadimidine often found in natural water was studied in laboratory experiments using four types of real wastewater. Ozonation was found to decrease the proportion of organic matter with a molecular weight greater than 5 kDa as well as protein-like, fulvic-like and humic-like components, but except the proportion of hydrophilic components. The aromaticity of the dissolved organic matter was also reduced after ozonation. The complexation of tryptophan and tyrosine with sulfadimidine mainly depends on their hydrophobicity and large molecular weight. Ozonation of fulvic and humic acid tends to produce small and medium molecular weight hydrophilics. The complexation of humic and fulvic acids with sulfadimidine was enhanced by ozonation. Dissolved organic matter, with or without oxidation, were found to weaken sulfadimidine’s inhibition of microbial growth, especially for Aeromonas and Acinetobacter species. This finding will expand our understanding about the impact of advanced treatment processes on the dissolved organic matters’ properties in effluent.

The application of low ozone dosage to minimize the problems caused by filamentous foaming was evaluated in two bioreactors of an urban wastewater treatment plant. Filamentous and nitrifying bacteria, as well as protist and metazoa, were monitored throughout a one-year period by FISH and conventional microscopy to examine the effects of ozone application on these specific groups of microorganisms. Multivariate data analysis was used to determine if the ozone dosage was a key factor determining the low carbon and nitrogen removal efficiencies observed throughout the study period, as well as to evaluate its impact on the biological communities monitored. The results of this study suggested that ozonation did not significantly affect the COD removal efficiency, although it had a moderate effect on ammonia removal efficiency. Filamentous bacteria were the community most influenced by ozone (24.9% of the variance explained by ozone loading rate), whilst protist and metazoa were less affected (11.9% of the variance explained). Conversely, ozone loading rate was not a factor in determining the nitrifying bacterial community abundance and composition, although this environmental variable was correlated with ammonia removal efficiency. The results of this study suggest that different filamentous morphotypes were selectively affected by ozone.

Antibiotics as emerging pharmaceutical pollutants have seriously not only threatened human life and animal health security, but also caused environmental pollution. It has drawn enormous attention and research interests in the study of antibiotics removal from aqueous environments. Graphene, an interesting one-atom-thick, 2D single-layer carbon sheet with sp² hybridized carbon atoms, has become an important agent for removal of antibiotic, owing to its unique physiochemical properties. Recently, a variety of graphene-based nanomaterials (GNMs) are reported to efficiently remove antibiotics from aqueous solutions by different technologies. In this review, we summarize different structure and properties of GNMs for the removal of antibiotics by adsorption. Meanwhile, advanced oxidation processes (AOPs), such as photocatalysis, Fenton process, ozonation, sulfate radical and combined AOPs by the aid of GNMs are summarized. Finally, the opportunities and challenges on the future scope of GNMs for removal of antibiotics from aqueous environments are proposed.