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.

Ozone as oxidizing agent for the total oxidizable precursor (TOP) assay and as a preceding step for activated carbon treatments concerning per- and polyfluoroalkyl substance removal.

Several thousands of highly persistent per- and polyfluoroalkyl substances (PFAS) exist and it is therefore challenging to analytically determine a larger spectrum of these compounds simultaneously in one sample. It is even more difficult to efficiently remove mobile PFAS in wastewater treatment plants (WWTPs) to protect the receiving waters. The total oxidizable precursor (TOP) assay is an approach that enables the detection of the total PFAS content in a sample via oxidation of precursors, followed by subsequent analysis of the perfluoroalkyl acid (PFAA) concentration before and after oxidative processes. Activated carbon combined with a preceding ozonation step is considered a promising tool for the removal of micropollutants but considering PFAS removal efficiencies in effluents for this process combination more information is required. The focus of the study was to implement and assess the TOP assay with ozone as oxidizing agent to estimate the total PFAS content in a WWTP effluent. Additionally, granular activated carbon (GAC) and powdered activated carbon (PAC) with a preceding ozonation step was tested for the removal efficiencies for 22 PFAS. For the TOP assay the obtained accordance in molarity using spiked tap water as quality control was 95.2% (15 mg O3/L) and 99.1% (6 mg O3/L). Applying the TOP assay, an estimated total PFAS content of 840 ng/L was determined in the respective effluent, which was 91.1% higher than obtained by target PFAS analysis, implying the presence of unknown precursors not included in common monitoring. While all treatment techniques that included ozone or a preceding ozonation step solely transformed precursors and long-chain perfluoroalkyl acids (PFAA, i.e., >C9) to shorter congeners, PAC was the only tested water treatment application that was able to remove 19.3% of the total PFAS molarity.

Genotoxic activities of wastewater after ozonation and activated carbon filtration: Different effects in liver-derived cells and bacterial indicators.

Aim of this study was to investigate the impact of advanced wastewater treatment techniques (combining ozonation with activated carbon filtration) on acute and genotoxic activities of tertiary treated wastewater. Concentrated samples were tested in Salmonella/microsome assays. Furthermore, induction of DNA damage was measured in liver-derived cells (human hepatoma and primary rat hepatocytes) in single cell gel electrophoresis experiments, which are based on the measurement of DNA migration in an electric field. These cell types possess phase I and phase II enzymes, which catalyze the activation/detoxification of mutagens. Acute toxicity was determined with the trypan blue exclusion technique. We found no evidence for mutagenic effects of non-ozonated samples in several bacterial tester strains (TA98, TA100, YG7108, YG7104, YG7112 and YG7113) but clear induction of His+ mutants after O3 treatment in two strains with defective genes encoding for DNA repair, which are highly sensitive towards alkylating agents (YG7108 and YG7104). These effects were reduced after activated carbon filtration. Furthermore, we detected a slight increase of mutagenic activity in strain YG1024 with increased acetyltransferase activity, which is sensitive towards aromatic amines and nitro compounds in untreated water, which was not reduced by O3 treatment. A completely different pattern of mutagenic activity was seen in liver-derived cells; non ozonated samples caused in both cell types pronounced DNA damage, which was reduced (by ca. 25%) after ozonation. Activated carbon treatment did not cause a substantial further reduction of DNA damage. Additional experiments with liver homogenate indicate that the compounds which cause the effects in the human cells are promutagens which require enzymatic activation. None of the waters caused acute toxicity in the liver-derived cells and in the bacterial indicators. Assuming that hepatic mammalian cells reflect the genotoxic properties of the waters in vertebrates (including humans) more adequately as genetically modified bacterial indicators, we conclude that ozonation has beneficial effects in regard to the reduction of genotoxic properties of treated wastewaters.

Best available technologies and treatment trains to address current challenges in urban wastewater reuse for irrigation of crops in EU countries.

Conventional urban wastewater treatment plants (UWTPs) are poorly effective in the removal of most contaminants of emerging concern (CECs), including antibiotics, antibiotic resistant bacteria and antibiotic resistance genes (ARB&ARGs). These contaminants result in some concern for the environment and human health, in particular if UWTPs effluents are reused for crop irrigation. Recently, stakeholders' interest further increased in Europe, because the European Commission is currently developing a regulation on water reuse. Likely, conventional UWTPs will require additional advanced treatment steps to meet water quality limits yet to be officially established for wastewater reuse. Even though it seems that CECs will not be included in the proposed regulation, the aim of this paper is to provide a technical contribution to this discussion as well as to support stakeholders by recommending possible advanced treatment options, in particular with regard to the removal of CECs and ARB&ARGs. Taking into account the current knowledge and the precautionary principle, any new or revised water-related Directive should address such contaminants. Hence, this review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403, who for three years have been constructively discussing the efficiency of the best available technologies (BATs) for urban wastewater treatment to abate CECs and ARB&ARGs. In particular, ozonation, activated carbon adsorption, chemical disinfectants, UV radiation, advanced oxidation processes (AOPs) and membrane filtration are discussed with regard to their capability to effectively remove CECs and ARB&ARGs, as well as their advantages and drawbacks. Moreover, a comparison among the above-mentioned processes is performed for CECs relevant for crop uptake. Finally, possible treatment trains including the above-discussed BATs are discussed, issuing end-use specific recommendations which will be useful to UWTPs managers to select the most suitable options to be implemented at their own facilities to successfully address wastewater reuse challenges.

Consolidated vs new advanced treatment methods for the removal of contaminants of emerging concern from urban wastewater.

Urban wastewater treatment plants (WWTPs) are among the main anthropogenic sources for the release of contaminants of emerging concern (CECs) into the environment, which can result in toxic and adverse effects on aquatic organisms and consequently on humans. Unfortunately, WWTPs are not designed to remove CECs and secondary (e.g., conventional activated sludge process, CAS) and tertiary (such as filtration and disinfection) treatments are not effective in the removal of most CECs entering WWTP. Accordingly, several advanced treatment methods have been investigated for the removal of CECs from wastewater, including consolidated (namely, activated carbon (AC) adsorption, ozonation and membranes) and new (such as advanced oxidation processes (AOPs)) processes/technologies. This review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403 who for three years have been constructively discussing the state of the art and the best available technologies for the advanced treatment of urban wastewater. In particular, this work critically reviews the papers available in scientific literature on consolidated (ozonation, AC and membranes) and new advanced treatment methods (mainly AOPs) to analyse: (i) their efficiency in the removal of CECs from wastewater, (ii) advantages and drawbacks, (iii) possible obstacles to the application of AOPs, (iv) technological limitations and mid to long-term perspectives for the application of heterogeneous processes, and (v) a technical and economic comparison among the different processes/technologies.

Optimization of ozonation and peroxone process for simultaneous control of micropollutants and bromate in wastewater.

The study aims to simultaneously control micropollutants and bromate formations by using ozonation and peroxone process. The batch experiments were run with variations in specific ozone dose (SOD) and hydrogen peroxide-to-ozone (H2O2/O3) ratio. Based on the removal by ozonation and peroxone, micropollutants were categorized into three groups: non-reactive compounds (i.e. amidotrizoate), moderately reactive compounds (i.e. metoprolol, acesulfame potassium, bezafibrate, and benzotriazole), and highly reactive compounds (i.e. carbamazepine and diclofenac). For ozonation and peroxone process, the removals for highly reactive compounds and moderately reactive compounds were 82-99% and 29-99%, respectively. The removal of amidotrizoate was not observed in this study. The effect of ozonation on micropollutant removals was similar to the peroxone process. However, differences in bromate formation were observed. Bromate formation depended on the SOD, while addition of hydrogen peroxide suppressed the bromate formation. The peroxone process at the H2O2/O3 ratio of 0.3 was recommended to bromide-containing water below 100 µg·L-1 for simultaneous control of micropollutants and bromate. Enhancement in micropollutant removals, except for the non-reactive groups, was achieved with either higher SOD or the addition of hydrogen peroxide to ozonation. The micropollutant removal predicted from the second-order kinetic reaction with ozone and •OH exposures was higher than the observed data.

Impact of ozonation on ecotoxicity and endocrine activity of tertiary treated wastewater effluent.

Tertiary wastewater treatment plant effluent before and after ozonation (0.6-1.1g O3/g DOC) was tested for aquatic ecotoxicity in a battery of standardised microbioassays with green algae, daphnids, and zebrafish eggs. In addition, unconjugated estrogen and 17ß-hydroxyandrogen immunoreactive substances were quantified by means of enzyme immunoassays, and endocrine effects were analysed in a 21-day fish screening assay with adult male and female medaka (Oryzias latipes). Ozonation decreased estrogen-immunoreactivity by 97.7±1.2% and, to a lesser extent, androgen-immunoreactivity by 56.3±16.5%. None of the short-term exposure ecotoxicity tests revealed any adverse effects of the tertiary effluent, neither before nor after the ozonation step. Similarly in the fish screening assay, reproductive fitness parameters showed no effects attributed to micropollutants, and no detrimental effects of the effluents were observed. Based on the presented screening, ozonation effectively reduced steroid hormone levels in the wastewater treatment plant effluent without increasing the effluent's ecotoxicity.

Micropollutant removal during biological wastewater treatment and a subsequent ozonation step.

The design criteria for wastewater treatment plants (WWTP) and the sludge retention time, respectively, have a significant impact on micropollutant removal. The upgrade of an Austrian municipal WWTP to nitrogen removal (best available technology, BAT) resulted in increased elimination of most of the analyzed micropollutants. Substances, such as bisphenol-A, 17alpha-ethinylestradiol and the antibiotics erythromycin and roxithromycin were only removed after the upgrade of the WWTP. Nevertheless, the BAT was not sufficient to completely eliminate these compounds. Thus, a pilot scale ozonation plant was installed for additional treatment of the effluent. The application of 0.6 g O(3) g DOC(-1) increased the removal of most of the micropollutants, especially for compounds that were not degraded in the previous biological process, as for example carbamazepine and diclofenac. These results indicated that the ozonation of WWTP effluent is a promising technology to further decrease emissions of micropollutants from the treatment process.