Influence of water matrix components on the UV/chlorine process and its reactions mechanism.

The UV/chlorine system has become an attractive alternative Advanced Oxidation Process (AOP) for the removal of recalcitrant pollutants in the last decade due to the simultaneous formation of chlorine and hydroxyl radicals. However, there is no consensus regarding the results and trends obtained in previous micropollutant removal studies by AOPs, highlighting the complexity of the UV/chlorine process and the need for further research. This study investigates the degradation of acetaminophen (ACTP) by UV/chlorine and the effects of the water matrix in the reaction kinetics. In particular, the effects of natural organic matter (NOM), alkalinity and mineral salts on the kinetics and reactive species were elucidated. The complexity of the system was revealed by the analysis of the radical generation and transformation in different water matrices, applying the kinetic modelling approach to complement the scavenger tests. The higher kinetic rates of ACTP at alkaline pH provided new insights into the chlorine reactions under UV radiation, where secondary and tertiary reactive oxygen species including ozone were proven to play the major role in degradation. On the contrary, at acidic pH, reaction kinetic modelling demonstrated that ClO• radical occurs at high concentrations in the order of 10-10 M, being therefore the main oxidant, followed by other chlorine radicals. It is noteworthy that at alkaline pH the presence of typical inorganic ions such as carbonate had little impact on ACTP degradation, contrary to the observed reduction of degradation rates at acidic pH. The expected detrimental effect of the NOM in AOPs was also evidenced, although the use of chlorine as radical source reduces the relevance of the inner filter effect in comparison to UV/H2O2.

Catalytic Ozonation of Pharmaceuticals Using CeO2-CeTiOx-Doped Crossflow Ultrafiltration Ceramic Membranes.

The removal of persistent organic micropollutants (OMPs) from secondary effluent in wastewater treatment plants is critical for meeting water reuse standards. Traditional treatment methods often fail to adequately degrade these contaminants. This study explored the efficacy of a hybrid ozonation membrane filtration (HOMF) process using CeO2 and CeTiOx-doped ceramic crossflow ultrafiltration ceramic membranes for the degradation of OMPs. Hollow ceramic membranes (CM) with a 300 kDa molecular weight cut-off (MWCO) were modified to serve as substrates for catalytic nanosized metal oxides in a crossflow and inside-out operational configuration. Three types of depositions were tested: a single layer of CeO2, a single layer of CeTiOx, and a combined layer of CeO2 + CeTiOx. These catalytic nanoparticles were distributed uniformly using a solution-based method supported by vacuum infiltration to ensure high-throughput deposition. The results demonstrated successful infiltration of the metal oxides, although the yield permeability and transmembrane flow varied, following this order: pristine > CeTiOx > CeO2 > CeO2 + CeTiOx. Four OMPs were examined: two easily degraded by ozone (carbamazepine and diclofenac) and two recalcitrant (ibuprofen and pCBA). The highest OMP degradation was observed in demineralized water, particularly with the CeO2 + CeTiOx modification, suggesting O3 decomposition to hydroxyl radicals. The increased resistance in the modified membranes contributed to the adsorption phenomena. The degradation efficiency decreased in secondary effluent due to competition with the organic and inorganic load, highlighting the challenges in complex water matrices.

Advanced oxidation processes for water and wastewater treatment - Guidance for systematic future research.

Advanced oxidation processes (AOPs) are a growing research field with a large variety of different process variants and materials being tested at laboratory scale. However, despite extensive research in recent years and decades, many variants have not been transitioned to pilot- and full-scale operation. One major concern are the inconsistent experimental approaches applied across different studies that impede identification, comparison, and upscaling of the most promising AOPs. The aim of this tutorial review is to streamline future studies on the development of new solutions and materials for advanced oxidation by providing guidance for comparable and scalable oxidation experiments. We discuss recent developments in catalytic, ozone-based, radiation-driven, and other AOPs, and outline future perspectives and research needs. Since standardized experimental procedures are not available for most AOPs, we propose basic rules and key parameters for lab-scale evaluation of new AOPs including selection of suitable probe compounds and scavengers for the measurement of (major) reactive species. A two-phase approach to assess new AOP concepts is proposed, consisting of (i) basic research and proof-of-concept (technology readiness levels (TRL) 1-3), followed by (ii) process development in the intended water matrix including a cost comparison with an established process, applying comparable and scalable parameters such as UV fluence or ozone consumption (TRL 3-5). Subsequent demonstration of the new process (TRL 6-7) is briefly discussed, too. Finally, we highlight important research tools for a thorough mechanistic process evaluation and risk assessment including screening for transformation products that should be based on chemical logic and combined with complementary tools (mass balance, chemical calculations).

Urban stormwater harvesting and reuse: a probe into the chemical, toxicology and microbiological contaminants in water quality.

Stormwater is one of the last major untapped urban water resources that can be exploited as an alternative water source in Australia. The information in the current Australian Guidelines for Water Recycling relating to stormwater harvesting and reuse only emphasises on a limited number of stormwater quality parameters. In order to supply stormwater as a source for higher value end-uses, a more comprehensive assessment on the potential public health risks has to be undertaken. Owing to the stochastic variations in rainfall, catchment hydrology and also the types of non-point pollution sources that can provide contaminants relating to different anthropogenic activities and catchment land uses, the characterisation of public health risks in stormwater is complex, tedious and not always possible through the conventional detection and analytical methods. In this study, a holistic approach was undertaken to assess the potential public health risks in urban stormwater samples from a medium-density residential catchment. A combined chemical-toxicological assessment was used to characterise the potential health risks arising from chemical contaminants, while a combination of standard culture methods and quantitative polymerase chain reaction (qPCR) methods was used for detection and quantification of faecal indicator bacteria (FIB) and pathogens in urban stormwater. Results showed that the concentration of chemical contaminants and associated toxicity were relatively low when benchmarked against other alternative water sources such as recycled wastewater. However, the concentrations of heavy metals particularly cadmium and lead have exceeded the Australian guideline values, indicating potential public health risks. Also, high numbers of FIB were detected in urban stormwater samples obtained from wet weather events. In addition, qPCR detection of human-related pathogens suggested there are frequent sewage ingressions into the urban stormwater runoff during wet weather events. Further water quality monitoring study will be conducted at different contrasting urban catchments in order to undertake a more comprehensive public health risk assessment for urban stormwater.

N-Nitrosamines and their precursors in wastewater effluents from selected industries in Spain.

N-nitrosamines (NAs), and N-nitrosodimethylamine (NDMA) in particular, are hazardous disinfection byproducts (DBPs) relevant when wastewater impacts drinking water sources and, in water reuse practices. Our study investigates the concentrations of NDMA and five additional NAs and their precursors in industrial wastewater effluents. Aiming to identify potential differences between industrial typologies, wastewaters from 38 industries belonging to 11 types of the UN International Standard Industrial Classification of All Economic Activities system (ISIC) were analysed. Results show that the presence of most NAs and their precursors cannot be linked to a specific industry type as these were in general very different within the classes. Nevertheless, N-nitrosomethylethylamine (NMEA) and N-nitrosopiperidine (NPIP) as well as precursors for N-nitrosodiethylamine (NDEA), NPIP and N-nitrosodibuthylamine (NDBA) could be rank with different concentrations between ISIC classes (p-value < 0.05). Specific industrial wastewater with notable high concentrations of NAs and their precursors were identified too. The effluents with the highest concentration of NDMA belong to the ISIC C2011 class (Manufacture of basic chemical), while the effluents with the highest concentration of NDMA precursors were from the ISIC C1511 class (Tanning and dressing of leather; dressing and dyeing of fur). Other relevant NAs found were NDEA in ISIC class B0810 (Quarrying of stone, sand, and clay) and ISIC class C2029 (Manufacture of other chemical products).

Degradation of diclofenac and 4-chlorobenzoic acid in aqueous solution by cold atmospheric plasma source.

In this study, cold atmospheric plasma (CAP) was explored as a novel advanced oxidation process (AOP) for water decontamination. Samples with high concentration aqueous solutions of Diclofenac sodium (DCF) and 4-Chlorobenzoic acid (pCBA) were treated by plasma systems. Atmospheric pressure plasma jets (APPJs) with a 1 pin-electrode and multi-needle electrodes (3 pins) configurations were used. The plasma generated using argon as working gas was touching a stationary liquid surface in the case of pin electrode-APPJ while for multi-needle electrodes-APPJ the liquid sample was flowing during treatment. In both configurations, a commercial RF power supply was used for plasma ignition. Measurement of electrical signals enabled precise determination of power delivered from the plasma to the sample. The optical emission spectroscopy (OES) of plasma confirmed the appearance of excited reactive species in the plasma, such as hydroxyl radicals and atomic oxygen which are considered to be key reactive species in AOPs for the degradation of organic pollutants. Treatments were conducted with two different volumes (5 mL and 250 mL) of contaminated water samples. The data acquired allowed calculation of degradation efficiency and energy yield for both plasma sources. When treated with pin-APPJ, almost complete degradation of 5 mL DCF occurred in 1 min with the initial concentration of 25 mg/L and 50 mg/L, whereas 5 mL pCBA almost degraded in 10 min at the initial concentration of 25 mg/L and 40 mg/L. The treatment results with multi-needle electrodes system confirmed that DCF almost completely degraded in 30 min and pCBA degraded about 24 % in 50 min. The maximum calculated energy yield for 50 % removal was 6465 mg/kWh after treatment of 250 mL of DCF aqueous solution utilizing the plasma recirculation technique. The measurements also provided an insight to the kinetics of DCF and pCBA degradation. Degradation products and pathways for DCF were determined using LC-MS measurements.

Could we estimate industrial wastewater flows composition using the UN-ISIC classification system?

Although we have extensive datasets on the location and typology of industries, we do not know much on their generated and discharged wastewater. This lack of information compromises the achievement of the sustainable development goals focused on water (Sustainable Development Goal 6) in Europe and globally. Thus, our goal was to assess to which degree the chemical composition of industrial wastewater could be estimated based on the industry's typology according to its International Standard Industrial Classification of All Economic Activities (ISIC) class. We collected wastewater effluent water samples from 60 industrial wastewater effluents (before any wastewater treatment process), accounting for 5 samples each of 12 ISIC classes, analyzed the composition of key contaminants (i.e. European Commission rated priority compounds and watchlist), and statistically assessed the similarities and differences amongst ISIC classes using ordination and random forest analyses. The results showed statistically significant linkages between most ISIC classes and the composition of produced wastewater. Among the analytical parameters measured, the random forest methodology allowed identifying a sub-set particularly relevant for classification or eventual contamination prediction based on ISIC class. This is an important applied research topic with strong management implications to (i) determine pollution emission caps for each individual ISIC class, (ii) define monitoring schemes to sample and analyze industrial wastewater, and (iii) enable predicting pollutant loads discharged in river basins with scarce information. These encouraging results urge us to expand our work into other ISIC classes and water quality parameters to draw a full picture of the relationship between ISIC classes and produced wastewater.

Effect of UV and UV/H2O2 in the presence of chloramines on NDMA formation potential of tramadol.

This study evaluates the effect of UV-C and UV-C/H(2)O(2) in the presence of chloramines on the N-nitrosodimethylamine formation potential (NDMA FP) of tramadol as a model precursor. The experiments were performed at high initial concentrations of TMDL (i.e., 20 mg/L) in order to elucidate the structures of TMDL byproducts. Twenty-four byproducts were identified in UV-C, UV-C/monochloramine, and UV/H(2)O(2)/monochloramine oxidation of tramadol using MS(3) capabilities of a hybrid quadrupole-linear ion trap mass spectrometer, combined with online hydrogen/deuterium (H/D) exchange experiments. Oxidative cleavage of methoxy and methoxybenzene moiety, O-demethylation, hydroxylation, and cyclohexane ring-opening were identified as major reaction mechanisms of tramadol in UV oxidation. Addition of monochloramine decreased the degradation rates of tramadol and its byproducts and yielded several monochlorinated derivatives. The oxidation rates were significantly enhanced in the presence of H(2)O(2), and byproducts of oxidative benzene ring-opening were detected. The majority of the identified byproducts are likely to have a higher NDMA FP than the parent compound due to a reduced steric hindrance and/or insertion of electron-donating hydroxyl groups in the N,N-dimethylamine side chain. This was confirmed by the results of NDMA FP tests, which showed that the formation of NDMA was enhanced up to four times depending on the process conditions in UV alone and in UV and UV/H(2)O(2) in the presence of monochloramine. Prolonged oxidation by hydroxyl radicals in UV/H(2)O(2)/monochloramine process mineralized some of the byproducts and slightly reduced the NDMA FP at the end of the treatment. The obtained degradation pathway of tramadol allowed the correlation of changes in NDMA FP during oxidation with its major oxidative transformation reactions. This manuscript demonstrates the significance of oxidation byproducts as NDMA precursors and emphasizes the need for their consideration when evaluating the evolution of NDMA FP during oxidative treatment.

Assessment of degradation byproducts and NDMA formation potential during UV and UV/H2O2 treatment of doxylamine in the presence of monochloramine.

UV-C radiation is the U.S. EPA recommended technology to remove N-nitrosodimethylamine (NDMA) during drinking and recycled water production. Frequently, H(2)O(2) is added to the treatment to remove other recalcitrant compounds and to prevent NDMA reformation. However, the transformation of NDMA precursors during the UV and UV/H(2)O(2) process and the consequences for NDMA formation potential are currently not well understood, in particular in the presence of monochloramine. In this study, doxylamine has been chosen as a model compound to elucidate its degradation byproducts in the UV and UV/H(2)O(2) process and correlate those with changes to the NDMA formation potential. This study shows that during UV treatment in the presence and absence of monochloramine, NDMA formation potential can be halved. However, an increase of more than 30% was observed when hydrogen peroxide was added. Ultrafast liquid chromatography coupled to quadrupole-linear ion trap mass spectrometer was used for screening and structural elucidation of degradation byproducts identifying 21 chemical structures from the original parent compound. This work shows that further oxidation of NDMA precursors does not necessarily lead to a decrease in NDMA formation potential. Degradation byproducts with increased electron density in the vicinity of the dimethylamino moiety, for example induced by hydroxylation, may have a higher yield of nucleophilic substitution and subsequent NDMA formation compared to the parent compound during chloramination. This work demonstrates the need to consider the formation of oxidation byproducts and associated implications for the control and management of NDMA formation in downstream processes and distribution when integrating oxidative treatments into a treatment train generating either drinking water or recycled water for potable reuse.

A decade of monitoring micropollutants in urban wet-weather flows: What did we learn?

Urban wet-weather discharges from combined sewer overflows (CSO) and stormwater outlets (SWO) are a potential pathway for micropollutants (trace contaminants) to surface waters, posing a threat to the environment and possible water reuse applications. Despite large efforts to monitor micropollutants in the last decade, the gained information is still limited and scattered. In a metastudy we performed a data-driven analysis of measurements collected at 77 sites (683 events, 297 detected micropollutants) over the last decade to investigate which micropollutants are most relevant in terms of 1) occurrence and 2) potential risk for the aquatic environment, 3) estimate the minimum number of data to be collected in monitoring studies to reliably obtain concentration estimates, and 4) provide recommendations for future monitoring campaigns. We highlight micropollutants to be prioritized due to their high occurrence and critical concentration levels compared to environmental quality standards. These top-listed micropollutants include contaminants from all chemical classes (pesticides, heavy metals, polycyclic aromatic hydrocarbons, personal care products, pharmaceuticals, and industrial and household chemicals). Analysis of over 30,000 event mean concentrations shows a large fraction of measurements (> 50%) were below the limit of quantification, stressing the need for reliable, standard monitoring procedures. High variability was observed among events and sites, with differences between micropollutant classes. The number of events required for a reliable estimate of site mean concentrations (error bandwidth of 1 around the "true" value) depends on the individual micropollutant. The median minimum number of events is 7 for CSO (2 to 31, 80%-interquantile) and 6 for SWO (1 to 25 events, 80%-interquantile). Our analysis indicates the minimum number of sites needed to assess global pollution levels and our data collection and analysis can be used to estimate the required number of sites for an urban catchment. Our data-driven analysis demonstrates how future wet-weather monitoring programs will be more effective if the consequences of high variability inherent in urban wet-weather discharges are considered.

Evaluation of contaminant removal of reverse osmosis and advanced oxidation in full-scale operation by combining passive sampling with chemical analysis and bioanalytical tools.

Advanced water treatment of secondary treated effluent requires stringent quality control to achieve a water quality suitable for augmenting drinking water supplies. The removal of micropollutants such as pesticides, industrial chemicals, endocrine disrupting chemicals (EDC), pharmaceuticals, and personal care products (PPCP) is paramount. As the concentrations of individual contaminants are typically low, frequent analytical screening is both laborious and costly. We propose and validate an approach for continuous monitoring by applying passive sampling with Empore disks in vessels that were designed to slow down the water flow, and thus uptake kinetics, and ensure that the uptake is only marginally dependent on the chemicals' physicochemical properties over a relatively narrow molecular size range. This design not only assured integrative sampling over 27 days for a broad range of chemicals but also permitted the use of a suite of bioanalytical tools as sum parameters, representative of mixtures of chemicals with a common mode of toxic action. Bioassays proved to be more sensitive than chemical analysis to assess the removal of organic micropollutants by reverse osmosis, followed by UV/H2O2 treatment, as many individual compounds fell below the quantification limit of chemical analysis, yet still contributed to the observed mixture toxicity. Nonetheless in several cases, the responses in the bioassays were also below their quantification limits and therefore only three bioassays were evaluated here, representing nonspecific toxicity and two specific end points for estrogenicity and photosynthesis inhibition. Chemical analytical techniques were able to quantify 32 pesticides, 62 PCPPs, and 12 EDCs in reverse osmosis concentrate. However, these chemicals could explain only 1% of the nonspecific toxicity in the Microtox assay in the reverse osmosis concentrate and 0.0025% in the treated water. Likewise only 1% of the estrogenic effect in the E-SCREEN could be explained by the quantified EDCs after reverse osmosis. In comparison, >50% of the estrogenic effect can typically be explained in sewage. Herbicidal activity could be fully explained by chemical analysis as the sampling period coincided with an illegal discharge and two herbicides dominated the mixture effect. The mass balance of the reverse osmosis process matched theoretical expectations for both chemical analysis and bioanalytical tools. Overall the investigated treatment train removed >97% estrogenicity, >99% herbicidal activity, and >96% baseline toxicity, confirming the suitability of the treatment train for polishing water for indirect potable reuse. The product water was indistinguishable from local tap water in all three bioassays. This study demonstrates the suitability and robustness of passive sampling linked with bioanalytical tools for semicontinuous monitoring of advanced water treatment with respect to micropollutant removal.

Climate change impact on EU rivers' dilution capacity and ecological status.

Impacts from urban wastewater treatment plants (WWTP) to receiving riverine surface water bodies (SWBs) depend on the load of contaminants discharged, as well as on their dilution capacity. Yet, climate change impacts on such dilution capacity and ultimately on the SWBs ecological status remain unclear. Here, we assess SWBs dilution capacity across the European continent to identify most vulnerable areas using information from centralized European databases. SWBs´ future dilution factor values are estimated based on representative concentration pathway scenarios impacts on rivers flow, and likely changes in European SWBs´ ecological status foretold. Results show that dilution factor in Europe increases by 5.4% in average. Yet, climate change effects are found to lead to a consistent dilution factor decrease for 11% of the 40074 European SWBs receiving WWTP discharge for the early century. This share reaches 17% for the midcentury period. We estimate that up to 42% of the SWBs receiving WWTP discharges and currently reaching a good ecological status show a 0.7 probability to have their ecological status downgraded due to climate change. Sites more vulnerable are located in the Mediterranean countries. Our findings highlight that climate change mitigation is essential for maintaining good ecological status in European SWBs.

Fate of N-nitrosodimethylamine and its precursors during a wastewater reuse trial in the Llobregat River (Spain).

In summer 2019, a full-scale trial was carried out to investigate the effects in drinking water quality when tertiary treated wastewater was discharged into the Llobregat River upstream of the intake of one of the major drinking water treatment plants of Barcelona and its metropolitan area. Two scenarios were investigated, i.e. discharging the reclaimed water with and without chemical disinfection with chlorine. This study investigates the concentration of N-nitrosodimethylamine (NDMA) as the specific disinfection conditions employed in this trial may favor its formation. To this aim, both NDMA and NDMA formation potential, were measured. The river contained NDMA at very low concentrations, but the concentration of NDMA precursors was already high. The NDMA concentration was reduced from discharge to the river to drinking water intake probably due to a combined effect of dilution and photolysis. The formation potential was also reduced probably due to dilution and biodegradation. The concentration of NDMA in the drinking water was always low (<7.3 ng/L), although the formation potential was above 10 ng/L in one sample. Dissolved organic matter characterization by high resolution mass spectrometry revealed differences between the nature of the organic matter in the river before and after reclaimed water discharge.

Fouling propensity of novel TFC membranes with different osmotic and hydraulic pressure driving forces.

The feasibility of Forward Osmosis (FO) as an alternative treatment technology to current membrane processes is believed to hinge on its reported lower fouling propensity. In this study, the impacts of constant osmotic pressure and hydraulic pressure driving forces on membrane fouling were investigated using a novel approach. In each case the cake layer was modelled accounting for all concentration polarisation effects and effective driving force. Compared to the widely employed method of using a non-constant osmotic pressure difference during bench-scale fouling experiments, maintaining a constant osmotic pressure led to 50% more alginate deposited on the same membrane surface (from 13.7 to 21.7 g/m2). This was attributed to a stronger osmotic driving force at the active layer interface and enhanced fouling due to a greater reverse flux of Na+ ions. An applied hydraulic pressure of 1 bar already changed fouling cake deposition and the cake structural parameter shrunk by 224 and 83 µm for the two thin-film composite membranes tested. A detailed analysis of the model however demonstrated that it needs further development, incorporating pore size, porosity and tortuosity of the foulant cake to enable drawing reliable conclusions on the causality of cake layer compaction.

Recovery of in-sewer dosed iron from digested sludge at downstream treatment plants and its reuse potential.

Iron-based coagulants are dosed in enormous amounts and play an essential role in various segments of our urban water infrastructure. In order for the water industry to become circular, a closed-loop management strategy for iron needs to be developed. In this study, we have demonstrated for the first time that in-sewer dosed iron, either in the form of FeCl3 or ferric-based drinking water sludge (Fe-DWS) as a means to combat sewer corrosion and odour, can be recovered in the form of vivianite in digested sludge in down-stream wastewater treatment plants. Importantly, about 92 ± 2% of the in-sewer dosed Fe was estimated to be bound in vivianite in digested sludge. A simple insertion of Neodymium magnet allowed to recover 11 ± 0.2% and 15.3 ± 0.08% of the vivianite formed in the digested sludge of the in-sewer dosed iron in the form of FeCl3 and Fe-DWS, respectively. The purity of recovered vivianite ranged between 70 ± 5% and 49 ± 3% for in-sewer dosed FeCl3 and Fe-DWS, respectively. Almost complete (i.e. 98 ± 0.3%) separation of Fe in the form of ferrihydrite was achieved from vivianite after alkaline washing. Subsequent batch experiments demonstrated that the recovered ferrihydrite can be directly reused for efficient sulfide control in sewers. At a ferrihydrite-Fe:S molar ratio of 1.2:1, sewage dissolved sulfide concentrations was reduced from 15 mgS/L to below 0.5 mgS/L within 1 h of reaction. Overall, the results obtained in our study flag a first step for utilities towards a closed-loop iron-based coagulant management approach.

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.

Effects of aging of ferric-based drinking water sludge on its reactivity for sulfide and phosphate removal.

Recent studies demonstrated the practical potential of multiple beneficial reuse of ferric-rich drinking water sludge (ferric DWS) for sulfide and phosphate removal in wastewater applications. In practice, ferric DWS is often stored on-site for periods ranging from days to several weeks (or even months), which may affect its reuse potential through changes in iron speciation and morphology. In this study, we investigated for the first time the impact of ferric DWS 'aging' time on the iron speciation and morphology and its subsequent impact on its reactivity and overall sulfide and phosphate removal capacity. A series of coagulation tests were conducted to generate ferric DWS of a practically relevant composition by using raw influent water from a full-scale drinking water treatment plant (DWTP). A comparison with ferric DWS from 8 full-scale DWTPs confirmed the similitude. The presence of akaganeite (ß-FeOOH) was detected in ferric DWS (through XRD analyses), independent of the DWS storage time. However, the morphology of akaganeite changed over time from a predominant poorly-crystalline phase in 'fresh' DWS (8 ± 0.1% of total Fe) to a highly crystalline phase (76 ± 3% of total Fe) at a sludge aging time of 30 days which was confirmed by means of Rietveld refinement in XRD analyses (n = 3). Subsequent batch tests showed that its sulfide removal capacity decreased significantly from 1.30 ± 0.02 mmol S/mmol Fe (day 1) to 0.60 ± 0.01 (day 30), a decrease of 54 % (p < 0.05). The level of crystallinity however had no impact on sulfide removal kinetics, most sulfide being removed within 10 minutes. Upon aeration of sulfide-loaded ferric DWS in activate sludge, amorphous iron oxides species were formed independent of the initial DWS crystallinity which resulted in efficient P removal at capacities similar to that of conventional FeCl3 dosing.

Photo-Fenton decomposition of chlorfenvinphos: determination of reaction pathway.

The purpose of this work was to determine the degradation products and pathway of chlorfenvinphos (CFVP) in water treated by photo-Fenton driven by solar irradiation, as well as to develop an analytical procedure for the degradation experiments. Degradation products and pathway were determined in a laboratory experimental setup. Routine water sample analysis was done by standard laboratory wet chemistry procedures and the use of laboratory equipment such as HPLC-UV and ionic chromatography (IC). Solid-phase extraction (SPE) was used to extract analytes from an aqueous matrix, and GC-MS was used to identify intermediate degradation products. The use of an HPLC-TOF-MS provided more results on degradation products and more insight was gained into how degradation takes place. In all experiments, strong mineralisation and degradation of CFVP was observed. CFVP and its degradation products, like 2,4-dichlorophenol, 2,4-dichlorobenzoic acid and triethylphosphate were decomposed into organic substances like acetate, formate, maleate, and inorganic ions like chloride and phosphate, within the detection limits (12.5 microg/L for CFVP in the GC-MS and 40 microg/L in HPLC-UV) of the equipment used. In fact, Cl(-) emerges in nearly stoichiometric concentrations and PO(4)(3)(-) is precipitated as FePO(4). The remarkably complete absence of chlorinated aliphatic substances and chlorinated acids leads to the conclusion that chlorine is removed very quickly, and that residual DOC does not correspond to any chlorinated compound.

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.