Multi-target assessment of advanced oxidation processes-based strategies for indirect potable reuse of tertiary wastewater: Fate of compounds of emerging concerns, microbial and ecotoxicological parameters.

Two advanced oxidation processes (AOPs), namely ozone/H2O2 and UV/H2O2, were tested at pilot scale as zero-liquid-discharge alternative treatments for the removal of microbiological (bacteria and viruses), chemical (compounds of emerging concern (CECs)) and genotoxic responses from tertiary municipal wastewater for indirect potable reuse (IPR). The AOP treated effluents were further subjected to granular activated carbon (GAC) adsorption and UV disinfection, following the concept of multiple treatment barriers. As a reference, a consolidated advanced wastewater treatment train consisting of ultrafiltration, UV disinfection, and reverse osmosis (RO) was also employed. The results showed that, for the same electrical energy applied, the ozone/H2O2 treatment was more effective than the UV/H2O2 treatment in removing CECs. Specifically, the ozone/H2O2 treatment, intensified by high pressure and high mixing, achieved an average CECs removal efficiency higher than UV/H2O2 (66.8% with respect to 18.4%). The subsequent GAC adsorption step, applied downstream the AOPs, further improved the removal efficiency of the whole treatment trains, achieving rates of 98.5% and 96.8% for the ozone/H2O2 and UV/H2O2 treatments, respectively. In contrast, the ultrafiltration step of the reference treatment train only achieved a removal percentage of 22.5%, which increased to 99% when reverse osmosis was used as the final step. Microbiological investigations showed that all three wastewater treatment lines displayed good performance in the complete removal of regulated and optional parameters according to both national and the European Directive 2020/2184. Only P. aeruginosa resulted resistant to all treatments with a higher removal by UV/H2O2 when higher UV dose was applied. In addition, E. coli STEC/VTEC and enteric viruses, were found to be completely removed in all tested treatments and no genotoxic activity was detected even after a 1000-fold concentration. The obtained results suggest that the investigated treatments are suitable for groundwater recharge to be used as a potable water source being such a procedure an IPR. The intensified ozone/H2O2 or UV/H2O2 treatments can be conveniently incorporated into a multi-barrier zero-liquid-discharge scheme, thus avoiding the management issues associated with the retentate of the conventional scheme that uses reverse osmosis. By including the chemical cost associated with using 11-12 mg/L of H2O2 in the cost calculations, the overall operational cost (energy plus chemical) required to achieve 50% average CECs removal in tertiary effluent for an hypothetical full-scale plant of 250 m3/h (or 25,000 inhabitants) was 0.183 €/m3 and 0.425 €/m3 for ozone/H2O2 and UV/H2O2 treatment train, respectively.

An innovative biofilter technology for reducing environmental spreading of emerging pollutants and odour emissions during municipal sewage treatment.

Wastewater treatment plants (WWTPs) are known sources of contaminants of emerging concern (CECs) spreading into the environment, as well as, of unpleasant odors. CECs represent a potential hazard for human health and the environment being pharmaceutical or biologically active compounds and they are acquiring relevance in European directives. Similarly, the public concern about odour emissions from WWTPs is also increasing due to the decreasing distance between WWTP and residential areas. This study focuses on the effectiveness of the recently developed MULESL technology (MUch LEss SLudge; WO2019097463) in removing CECs and limiting odour emissions from WWTPs. MULESL technology has been developed for its ability to reduce up to 80% the sludge production from WWTPs. However, it is ought to evaluate if the benefits coming from sludge production reduction do not invalidate CECs removal or negatively affect odour emissions. Thus, the performances of a MULESL and a conventional WWTP (flow rate of 375 m3/d and 3600 m3/d, respectively) were compared while treating the same municipal sewage. Whereas both plants succeeded in removing the traditional gross parameters characterizing wastewaters (e.g. chemical oxygen demand, nitrogen), the MULESL was much more effective than the conventional one in terms of CECs removal for about 60% of the identified compounds showing, however, the same or lower effectiveness for about 30% and 10% of them, respectively. This result was attributed to the high sludge retention time and biomass concentration in the MULESL (enabling enrichment of slow growing microorganisms and forcing biomass to use unusual substrates, respectively), and to the biomass feature to grow in the form of biofilm and granules (favoring micropollutants absorption on biomass). Furthermore, odour impact analysis has shown that the MULESL was characterized by a much lower impact, i.e. 45% lower than that of primary and secondary treatments of the conventional WWTP.

Comparison of different types of landfill leachate treatments by employment of nontarget screening to identify residual refractory organics and principal component analysis.

Three different chemical oxidation processes were investigated in terms of their capability to degrade organic chemical components of real mature landfill-leachate in combination with biological treatment run in a Sequencing Batch Biofilter Granular Reactor (SBBGR). H2O2, H2O2 + UV and O3 were integrated with SBBGR and respective effluents were analyzed and compared with the effluent obtained from biological SBBGR treatment alone. In agreement with their respective oxidative power, conventional bulk parameters (residual COD, TOC, Ntot, TSS) determined from the resulting effluents evidenced the following efficacy ranking for degradation: SBBGR/O3 > SBBGR/UV + H2O2 > SBBGR/H2O2 > SBBGR. A more detailed characterization of the organic compounds was subsequently carried out for the four treated streams. For this, effluents were first subjected to a sample preparation step, allowing for a classification in terms of acidic, basic, strongly acidic and strongly basic compounds, and finally to analysis by liquid chromatography/high resolution mass spectrometry (LC/HR-MS). This classification, combined with further data post-processing (non-target screening, Venn Diagram, tri-dimensional plot and Principal Component Analysis), evidenced that the SBBGR/H2O2 process is comparable to the pure biological oxidation. In contrast, SBBGR/O3 and SBBGR/UV + H2O2 not only resulted in a very different residual composition as compared to SBBGR and SBBGR/H2O2, but also differ significantly from each other. In fact, and despite of the SBBGR/O3 being the most efficient process, this treatment remained chemically more similar to SBBGR/H2O2 than to SBBGR/UV + H2O2. This finding may be attributable to different mechanism of degradation involved with the use of UV radiation. Apart from these treatment differences, a series of recalcitrant compounds was determined in all of the four treatments and partly identified as hetero-poly-aromatic species (humic acids-like species).

Gross parameters prediction of a granular-attached biomass reactor by means of multi-objective genetic-designed artificial neural networks: touristic pressure management case.

The Artificial Neural Networks by Multi-objective Genetic Algorithms (ANN-MOGA) model has been applied to gross parameters data of a Sequencing Batch Biofilter Granular Reactor (SBBGR) with the aim of providing an effective tool for predicting the fluctuations coming from touristic pressure. Six independent multivariate models, which were able to predict the dynamics of raw chemical oxygen demand (COD), soluble chemical oxygen demand (CODsol), total suspended solid (TSS), total nitrogen (TN), ammoniacal nitrogen (N-NH4 (+)) and total phosphorus (Ptot), were developed. The ANN-MOGA software application has shown to be suitable for addressing the SBBGR reactor modelling. The R (2) found are very good, with values equal to 0.94, 0.92, 0.88, 0.88, 0.98 and 0.91 for COD, CODsol, N-NH4 (+), TN, Ptot and TSS, respectively. A comparison was made between SBBGR and traditional activated sludge treatment plant modelling. The results showed the better performance of the ANN-MOGA application with respect to a wide selection of scientific literature cases.

A single-stage biological process for municipal sewage treatment in tourist areas.

This pilot scale study aims to test the effectiveness of an innovative compact biological system (SBBGR - Sequencing Batch Biofilter Granular Reactor) for treating municipal wastewater in tourist areas characterised by intense seasonal water demand and wastewater discharge. The results obtained after a long term operation of 463 days have shown that the proposed system is able to assure average removal efficiencies higher than 90% for COD (chemical oxygen demand), total suspended solids and TKN (total Kjeldahl nitrogen) independently of the influent concentration values and organic loading, which ranged from 0.2 to 5.1 kgCOD/m(3)biofilter.d Furthermore, the plant showed a high degree of operation flexibility and stability in response to the organic load variations occurring in tourist areas. In fact, no significant deterioration in the plant's effluent quality was observed even during a sudden several-fold increase in organic loading. High nitrogen removal efficiencies (80%, on average) were also achieved thanks to the establishment of simultaneous nitrification-denitrification process favoured by the plant's high biomass concentration and operating conditions. Finally, the system was characterized by an excess sludge production much lower (60-80% lower) than that of conventional biological systems operating without a primary clarifier. An acceptable level of stabilization of excess sludge was also obtained so that a further stabilization process was no longer required.

Landfill wall revegetation combined with leachate recirculation: a convenient procedure for management of closed landfills.

There is a need for a reliable sustainable option to effectively manage the landfill leachate generation. This study presents a simple procedure for the revegetation of the walls of closed landfills, employing the leachate as a fertirrigant. The native plants Lepidium sativum, Lactuca sativa, and Atriplex halimus, which suit the local climate, were chosen for this study in Southern Italy. The methodology was structured into three phases (i) early stage toxicity assessment phase (apical root length and germination tests), (ii) adult plant resistance assessment phase, and (iii) soil properties verification phase. The rationale of the proposed approach was first to look at the distinctive qualities and the potential toxicity in landfill leachates for fertigation purposes. Afterwards, through specific tests, the plants used were ranked in terms of resistance to the aqueous solution that contained leachate. Finally, after long-term irrigation, any possible worsening of soil properties was evaluated. The results demonstrated the real possibility of using blended leachate as a fertigant for the revegetation of the walls of closed landfills. In particular, the plants maintained good health when leachate was blended at concentrations of lower than 25 and 5%, respectively for A. halimus and Lepidium sativum. Irrigation tests showed good resistance of the plants, even at dosages of 112 and 133.5 mm m(-2), at maximum concentrations of 25 and 5%, respectively, for A. halimus and Lepidium sativum. The analysis of the total chlorophyll content and of aerial parts dried weight confirmed the results reported above.

Is a sequencing batch biofilter granular reactor suitable for textile wastewater treatment?

The textile industry releases highly polluted and complex wastewaters, which are difficult to treat and require numerous treatment steps. Innovative technologies for on-site treatment at each factory would permit cost reduction. For this reason, we ran a laboratory-scale study to assess the suitability of a sequencing batch biofilter granular reactor (SBBGR) for textile wastewater treatment, testing four different types of wastewater. Results demonstrate that wastewater characteristics greatly affect the reactor efficiency. Hence, a pre-study is advisable to define the best operational conditions and the maximum treatment capability for the wastewater under analysis. Nevertheless, SBBGR is a valuable biological treatment, effective in the reduction of pollutant load with stable performances despite the variability in wastewater composition. Tests with ozone integration have demonstrated that it is possible to dose small quantities of ozone to obtain an effluent suitable for direct discharge. However, a dynamic ozone dosage should be used to optimize the process as the correct ozone dose strongly depends on the wastewater composition.

Granular biomass structure and population dynamics in Sequencing Batch Biofilter Granular Reactor (SBBGR).

The aim of this paper is to study the microbial and structural changes occurring during the transition from flocculent (used as inoculum) to biofilm and granular sludge in a Sequencing Batch Biofilter Granular Reactor (SBBGR). SBBGR is a new and promising technology characterised by low sludge production (5-6 times lower than in conventional treatment plants), high biomass concentration (up to 35 g TSS/L(bed)), high COD conversion capacity, high effluent quality and operation flexibility. Molecular in situ detection methods and microscopy staining procedures were employed in combination with the traditional measurements (i.e., oxygen uptake rate, COD removal efficiency) to evaluate the microbial activity and composition of the granular biomass. The granules structure was investigated by electron scanning microscopy, phase contrast analysis of granule sections and specific extracellular polymeric substances (EPS) stainings. Evident changes in biomass composition was observed during the shift from activated to granular sludge while a stable presence of active bacterial populations (mainly Proteobacteria) was found within mature granules.

Municipal wastewater treatment by a periodic biofilter with granular biomass.

The paper reports the results obtained during an experimental campaign aimed at transferring aerobic granulation to a demonstrative SBBGR system (i.e., a submerged biofilter that operates in a "fill and draw" mode) for the treatment of municipal wastewater by financial support of the European Commission, within the framework of Life-Environment Programme (PERBIOF Project; www.perbiof-europe.com). The results show that following the generation of granular biomass during the start-up period, the SBBGR was able to remove 80-90% of COD, total suspended solids and ammonia occurring in primary effluent from a municipal wastewater treatment plant even when the minimum hydraulic residence time (i.e., 4 h) was investigated. The process was characterised by a sludge production almost one magnitude order lower than commonly reported for conventional treatment plants. The granular biomass was characterised by a high density (i.e., 150 gTSS/L(biomass)) that allowed a biomass concentration as high as 35 kgTSS/m(3)(bed) to be achieved. Proteobacteria were found as main microbial components of the granular biomass by applying Fluorescence In Situ Hybridization (FISH). No significant changes in microbial composition were observed during reactor operation.

Removal of endocrine disrupter compounds from municipal wastewater by an innovative biological technology.

The removal of selected endocrine disrupter compounds (EDCs), namely estrone(E1), 17beta-estradiol (E2), 17alpha-ethynylestradiol (EE2), bisphenol A (BPA) and 4-tert-octylphenol (4t-OP) from municipal wastewater was investigated using a sequencing batch biofilter granular reactor (SBBGR), a new system for biological treatment based on aerobic granular biomass. This new biological treatment is characterized by high biomass concentration (up to 40 g/L), high sludge retention times (up to 6 months) and low sludge production (i.e., an order of magnitude lower than commonly reported for conventional biological technologies). The investigation was carried out comparing a demonstration SBBGR system with a conventional full-scale activated sludge process. Results showed that the SBBGR performed better than a conventional activated sludge process in removing E1, E2, BPA and 4t-OP. In fact, the average removal percentages of the above mentioned EDCs, obtained during a four month operating period, were 62.2, 68, 91.8, 77.9% and 56.4, 36.3, 71.3, 64.6% for the demonstrative SBBGR system and the conventional activated sludge process of the municipal sewage treatment plant, respectively.

Technological transfer to demonstrative scale of sequencing batch biofilter granular reactor (SBBGR) technology for municipal and industrial wastewater treatment.

The paper reports the results of an experimental investigation aimed at transferring to demonstrative scale an innovative technology (SBBGR-Sequencing Batch Biofilter Granular Reactor) for the treatment of municipal and industrial wastewater by financial support of the EU Life programme. When this technology was applied for treating municipal wastewater, the results showed that the system was able to remove 80-90% of COD, total suspended solids and ammonia independently of the hydraulic residence time investigated (i.e., from 12 to 4 h). In the case of tannery wastewater, chosen as representative of concentrated industrial wastewater, SBBGR technology was suitable for removing 80-90% of the COD, suspended solids and ammonia content up to organic loading values of 3.5 kg COD/m3.d. During both periods, the process was characterised by a very high sludge age value (theta(c) approximately 150 d) that led to a biomass concentration as high as 35 gTSS/L(bed) and a sludge production much lower (5-6 times lower) that than commonly reported for conventional treatment plants.

An innovative technology based on aerobic granular biomass for treating municipal and/or industrial wastewater with low environmental impact.

The paper reports the results of an investigation carried out at lab scale to assess the effectiveness of an innovative technology (SUPERBIO) for treating municipal and/or industrial wastewater. When this technology was applied for treating municipal wastewater, the results showed that even at maximum organic load (i.e. 7 kg COD m(-3) d(-1)), the COD in the treated effluent was lower than 50 mg L(-1). In addition, both ammonia and TKN removal efficiencies resulted in higher than 87% up to an organic load of 5.7 kg COD m(-3) d(-1) corresponding to a nitrogen load of 0.8 kg TKN m(-3) d(-1). Very satisfactory process performances also resulted during tannery wastewater treatment, when a chemical oxidation step (i.e. ozonation) was inserted in the treatment cycle of SUPERBIO. In such an instance, at organic and nitrogen loadings of 3 kgCOD m(-3) d(-1) and 0.20 kg N m(-3) d(-1), COD, NH4+ -N and TSS average removals were 96, 99 and 98%, respectively. Finally, during the whole experimentation, SUPERBIO was always characterised by a very low sludge production. Such a result was ascribed mainly to the characteristics of biomass that grew in the form of very dense granules (i.e. 130 gVSS L(Biomass)(-1) allowing a biomass concentration as high as 50-60 gTSS l(bed)(-1) to be achieved.

Hydraulic shear stress calculation in a sequencing Batch biofilm reactor with granular biomass.

This paper reports the results of an experimental study specifically aimed at developing a simple methodology for calculating hydrodynamic shear forces in a sequencing batch biofilm reactor (SBBR) system with granular biomass. Using such a methodology, the hydrodynamic shear forces are simply calculated by measuring bed porosity and pressure losses. In addition, by applying this methodology an explanation for the biomass evolution from biofilm to granules under aerobic conditions has been provided and the following mechanism has been proposed: (i) formation of a thin biofilm that fully covers the carrier; (ii) increase of biofilm thickness; (iii) break-up of the attached biofilm with release of biofilm particles; (iv) rearrangement of biofilm particles in smooth granules. The hydrodynamic shear forces trend during the start-up period provides an explanatory key for the generation process of granular biomass. In fact, during the first two steps, the SBBR is characterized by rather weak shear forces values (lower than 1 dyn/cm2). Under these weak shear forces, the biofilm grows by increasing its thickness through a porous structure and weak adhesion strengths. Such a continuous increase of biofilm thickness produces an increase of the shear forces with negative effect on biomass stability, causing the detachment of biofilm particles. In turn, such detachment causes a further sharp increase of shear forces (more than 10 times) that promotes the rearrangement of the detached biofilm particles in smooth granules. A correlation between biomass density and hydrodynamic shear forces was observed. In particular, the biomass density linearly increases with the increase of shear stress.

Integration of chemical and biological oxidation in a SBBR for tannery wastewater treatment.

This paper reports the results of an investigation aimed at evaluating the laboratory-scale performance of an innovative process for treating tannery wastewater. In this process, biological degradation, carried out in a sequencing batch biofilm reactor (SBBR), is combined with chemical oxidation by ozone. Tannery wastewater treatment was carried out, at laboratory scale, on a real primary effluent coming from a centralised plant treating wastewater produced by a large tannery district in Northern Italy. SBBR performance both without and with ozonation, was assessed with very satisfactory results. In particular, in the latter instance the recorded COD, TKN and TSS average removals, (96%), (92%) and (98%) respectively, allowed the maximum allowable concentration values fixed by the Italian regulation in force to be achieved without any additional polishing step. During the investigation biofilm properties (biofilm concentration and biofilm density) and flow dynamics aspects (head loss, shear stress, bed porosity) were also studied. A major feature of the process is that, with or without ozonation, it was characterised by very low specific sludge production (0.05 kgVSS/kgCODremoved) and high biofilm density (i.e. 87-122 gVSS/Lsludge) both contributing to a rather high biofilm concentration (i.e. 31-44 gTSS/Lfilter).

Tannery wastewater treatment by sequencing batch biofilm reactor.

The paper reports the results of an investigation aimed to evaluate the performances of an innovative process for treating tannery wastewater. In such a process biological degradation, carried out in a sequencing batch biofilm reactor (SBBR), is combined with chemical oxidation by ozone. The treatment was carried out at laboratory scale on a real primary effluent coming from a centralized plant treating the wastewater of a large tannery district in Northern Italy. SBBR performances without and with ozonation were compared with very satisfactory results particularly in the latter instance when the recorded COD, TKN, and TSS average removals, (96%), (92%), and (98%), respectively, permitted to achieve the fixed limits enforced by Italian regulation without needing any additional polishing step. With or without ozonation, the process that resulted was characterized by a specific sludge production (0.1 kgVSS/kg CODremoved) significantly lower than the values featuring conventional biological systems (i.e., 0.3-0.5 VSS/kg CODremoved). Moreover, as in the reactor the biomass density results were very high, i.e., 98 gVSS/Lsludge, it was possible to achieve and maintain biomass concentration as high as 20 gVSS/L.

Combined chemical and biological degradation of tannery wastewater by a periodic submerged filter (SBBR).

The paper reports on the results of an investigation aimed to evaluate the performances of an innovative tannery wastewater process based on the combining biological degradation, carried out in a sequencing batch biofilm reactor, with chemical oxidation, performed by ozone. The combined treatment was carried out at the laboratory scale on real primary effluent coming from a centralised plant treating the wastewater from a large tanning district in Northern Italy. SBBR performances with and without ozonation were compared resulting to be very satisfactory only in the latter instance where recorded COD, NH4-N and TSS average removals were 97%, 98% and 99.9%, respectively. Such efficiencies correspond to specific concentrations in treated effluent well below the limit values fixed by the in-force Italian regulations. Furthermore, it was proved that the combined process is characterised by a very low sludge production. In fact, the measured specific sludge production (0.03 kg TSS/kg COD(removed)) resulted unexpectedly much more lower than the value reported for conventional biological systems (i.e., 0.3-0.5 kg TSS/kg COD(removed)).

Treatment options for tannery wastewater. I: Alkalinization with or without post-ozonation.

This is the first of two papers each dealing with a specific technological option for replacing the Fenton's reagent with simpler processes for treating industrial wastewater. In particular, the paper reports the results of an investigation aimed to check, at lab scale, the effectiveness of a chemical process (i.e., alkalinisation with or without post-ozonation) for treating tannery wastewater whose residual COD, measured after conventional biological treatment, result still higher than the Italian COD Maximum Allowable Concentration (MAC) value (i.e., 160 mgO2/L). The results have demonstrated that when the value of residual COD lies in the range 200 divided by 250 mgO2/L, a simple alkalinisation with NaOH, up to pH 12.5, allows to reach the MAC value with an alkali consumption equivalent to the acid consumption required by the Fenton treatment and with a chemical sludge production significantly lower, i.e. approximately 0.7 kg(dry)/m3 instead of approximately 1.5 kg(dry)/m3. Conversely, when the value of the residual COD lies in a higher range (i.e. 300 divided by 350 mgO2/L), in order to reach the COD MAC value, alkalinisation (from pH 8 to pH 12.5) must be followed by an ozonation post-treatment. From the chemical stand point, the paper clearly demonstrates that analyzing only simple "gross parameters" (i.e., TSS, TOC, COD, BOD5 and EC20) it is possible to get useful information about the chemical properties of the organic pollutants occurring in tannery wastewater.