Extracellular polymeric substances as paper coating biomaterials derived from anaerobic granular sludge.

Recovering extracellular polymeric substances (EPS) from waste granular sludge offers a cost-effective and sustainable approach for transforming wastewater resources into industrially valuable products. Yet, the application potential of these EPS in real-world scenarios, particularly in paper manufacturing, remains underexplored. Here we show the feasibility of EPS-based biomaterials, derived from anaerobic granular sludges, as novel coating agents in paper production. We systematically characterised the rheological properties of various EPS-based suspensions. When applied as surface sizing agents, these EPS-based biomaterials formed a distinct, ultra-thin layer on paper, as evidenced by scanning electron microscopy. A comprehensive evaluation of water and oil penetration, along with barrier properties, revealed that EPS-enhanced coatings markedly diminished water absorption while significantly bolstering oil and grease resistance. Optimal performance was observed in EPS variants with elevated protein and hydrophobic contents, correlating with their superior rheological characteristics. The enhanced water-barrier and grease resistance of EPS-coated paper can be attributed to its non-porous, fine surface structure and the functional groups in EPS, particularly the high protein content and hydrophobic humic-like substances. This research marks the first demonstration of utilizing EPS from anaerobic granular sludge as paper-coating biomaterials, bridging a critical knowledge gap in the sustainable use of biopolymers in industrial applications.

Modelling and prediction of the effect of operational parameters on the fate of contaminants of emerging concern in WWTPs.

Wastewater treatment plants (WWTPs) provide a barrier against the discharge of contaminants of emerging concern (CECs) into the environment. The removal of CECs is highly WWTP-specific and the underlying mechanisms are still poorly understood, hampering the optimization of biological treatment steps for their removal. To fill this knowledge gap, we assessed the influence of four operational parameters of activated sludge biological treatment, namely total suspended solids, temperature, pH and redox conditions, on the sorption and biodegradation of four CECs under controlled laboratory conditions. Design of Experiments was used to better address the factors influencing CECs removal and interactions among operational parameters. The derived statistical models showed results in concordance with previous studies and indicated how sorption and biodegradation of the investigated CECs depend on most tested parameters and few of their interactions. The predictions of the developed models have been compared with literature values, indicating how the tested parameters are responsible for most of the variability of sorption, while they could not reliably generalize biodegradation rates. The developed models were also implemented as an extension of a mechanistic biological treatment model, successfully describing the dynamic behaviour of a large-scale WWTP, which was observed during a three-day continuous monitoring campaign. Compared to a traditional modelling approach, the one including the developed models showed on average almost a three-fold uncertainty reduction, favouring its use to aid WWTP managers and regulators for improved assessment of CEC fate and removal. Finally, the models highlighted that, while higher temperatures and solids concentrations generically favoured CECs removal, removal efficiency vary significantly due to operational parameters and no globally optimum conditions for CECs removal exist. The use of these models opens the door to the combined dynamic management of both traditional contaminants and CECs in WWTPs.

Integrated Exposure and Algal Ecotoxicological Assessments of Effluents from Secondary and Advanced-Tertiary Wastewater-Treatment Plants.

The great concern over the environmental impact of wastewaters has led to the designing of advanced treatment processes to upgrade conventional treatment plants and achieve a significant reduction of contaminants in receiving waters. In the present study we combined chemical and ecotoxicological analyses, aiming to evaluate the reduction of toxicity effects associated with the removal of micropollutants and to define the contribution of the detected compounds to the overall toxicity of the mixtures in a series of wastewater effluents collected from a secondary treatment (OUT 2) and from a tertiary activated carbon treatment (OUT 3) plant. The target compounds were selected after a screening procedure among pharmaceuticals, musk fragrances, and trace metals. The classical algal growth inhibition test was conducted on the original effluent samples and on different fractions obtained by solid-phase extraction (SPE) treatment. A good accordance was found between the removal of toxicity (30%-80%) and organic compounds (70%-80%) after the tertiary treatment, suggesting its high efficiency to improve the wastewater quality. The discrepancy between the contribution to the overall toxicity of the nonadsorbable compounds (i.e., inorganic or very polar organic compounds) as experimentally measured by the SPE bioassays (18%-76%) and calculated by the concentration addition approach (>97%) could be mitigated by including the bioavailability correction in metal-toxicity modeling of wastewater mixtures. For the organic compounds, the toxic equivalency method enabled us to quantify the portion of toxicity explained by the detected chemicals in both OUT 2 (82%-104%) and OUT 3 (5%-57%), validating the selection of the target molecules. The applied integrating approach could be implemented by the inclusion of both additional target chemicals and toxicity endpoints. Environ Toxicol Chem 2022;41:2404-2419. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Reuse of Water in Laundry Applications with Micro- and Ultrafiltration Ceramic Membrane.

This study compares the performance of a microfiltration membrane, made by silicon carbide (SiC) and an ultrafiltration membrane, made by zirconia (ZrO2), in the treatment of wastewater from a washing machine designed to clean industrial tents. The filtration of deionized water, containing model microplastics (i.e., nylon fiber), was performed. This was followed by the filtration of real wastewater from a single washing cycle of industrial tents, made from polyvinyl chloride (PVC) textile. The filtration parameters of the membranes and physical-chemical parameters of the wastewater, including the concentration of microplastics in the shape of tent fibers (PVC), were calculated before and after filtration. The microfiltration membrane manifested a greater decrease in permeability (95%) compared to the ultrafiltration membrane (37%). The resulting water quality in terms of Total Solids, turbidity, and microplastics concentration was better for the ultrafiltration. This is evident from 99.2% versus 98.55% removal efficiency of microplastics from the laundering wastewater, respectively.

Evaluation of the anaerobic degradation of food waste collection bags made of paper or bioplastic.

The amount of compostable bioplastics collected with the food waste is constantly growing, particularly due to the bags used for collection. According to the Italian legislation, compostable bioplastics must be accepted by all biological treatment plants, including aerobic and anaerobic facilities. Anyway, the compostability standard requires only the assessment of the aerobic degradability, while it is generally not required to test the behaviour under anaerobic conditions. This aspect is evaluated in the paper, where the anaerobic degradability of bioplastic bags used for the food waste collection is assessed. First, Biochemical Methane Potential (BMP) tests were performed on four commercial types of bioplastic bags, including those designed only for the collection of food waste and the shoppers, that can be reused for the same purpose. Subsequently, an innovative approach for this kind of substrate was applied, subjecting two bags to semi-continuous co-digestion tests together with the food waste. Both tests were performed by comparing the behaviour of bioplastic bags with that of an alternative collection paper bag. Finally, tests to evaluate the influence of physical phenomena on the degradation of bioplastics were performed to better understand the results of biological tests. BMP tests indicated a good degradability (>71%) of bioplastic bags, while semi-continuous tests showed a much lower degradability (<27%), confirmed by the observation of the undigested bag pieces. On the contrary, the paper bag presents interesting characteristics, because its degradability in the semi-continuous tests (82%) resulted even higher than that observed in the BMP tests (74%). These results highlight an important difference between the bags mono-digestion by means of BMP tests and the semi-continuous co-digestion tests with food waste, which better simulate the full-scale operational conditions.

Assessment of a simple and replicable procedure for selective phosphorus recovery from sewage sludge ashes by wet chemical extraction and precipitation.

The selective phosphorus recovery by wet chemical extraction and precipitation was assessed at the laboratory scale aiming at identifying a simple and replicable procedure that could be effectively applied to different types of sewage sludge ashes. The experimental work was performed on five samples of sewage sludge ashes, of which three were obtained from muffle-furnace incineration and two from full-scale mono-incineration plants. A single-step extraction procedure has been investigated by applying different operating conditions (type of leaching acid, liquid-to-solid ratio, contact time). Experimental results indicated that phosphorus recovery efficiency varied between 54 and 92% with limited co-dissolution of metals and metalloids, except for arsenic. Operating conditions, sewage sludge ashes characteristics and phosphorus removal processes in the wastewater treatment plant were the main factors affecting phosphorus recovery efficiency. The application of optimal operating conditions (0.2 M sulfuric acid, liquid-to-solid ratio of 20 and contact time of 2 h) resulted in phosphorus recovery from 76 to 92% on four samples. Subsequently, precipitation of phosphorus from acidic leachate was carried out by lime dosing. After filtering and drying, the recovered products presented a P2O5 content between 11.5 and 36.7% dry weight, with a fraction of soluble phosphorus between 75 and 91%, a good percentage for application as fertilizer or animal feed. Since few undesired elements (i.e., As, Cu and Zn) exceeded the limits for fertilizer application (exception was represented by Ni and Pb, which were present at low concentration), an additional purification step may be required. Overall, experimental results highlighted the influence of process parameters on phosphorus recovery.

Performance Analysis and Microbial Community Evolution of In Situ Biological Biogas Upgrading with Increasing H2/CO2 Ratio.

The effect of the amount of hydrogen supplied for the in situ biological biogas upgrading was investigated by monitoring the process and evolution of the microbial community. Two parallel reactors, operated at 37°C for 211 days, were continuously fed with sewage sludge at a constant organic loading rate of 1.5 gCOD∙(L∙d)-1 and hydrogen (H2). The molar ratio of H2/CO2 was progressively increased from 0.5 : 1 to 7 : 1 to convert carbon dioxide (CO2) into biomethane via hydrogenotrophic methanogenesis. Changes in the biogas composition become statistically different above the stoichiometric H2/CO2 ratio (4 : 1). At a H2/CO2 ratio of 7 : 1, the methane content in the biogas reached 90%, without adversely affecting degradation of the organic matter. The possibility of selecting, adapting, and enriching the original biomass with target-oriented microorganisms able to biologically convert CO2 into methane was verified: high throughput sequencing of 16S rRNA gene revealed that hydrogenotrophic methanogens, belonging to Methanolinea and Methanobacterium genera, were dominant. Based on the outcomes of this study, further optimization and engineering of this process is feasible and needed as a means to boost energy recovery from sludge treatment.

Extracellular biopolymers recovered as raw biomaterials from waste granular sludge and potential applications: A critical review.

Granular sludge (GS) is a special self-aggregation biofilm. Extracellular polymeric substances (EPS) are mainly associated with the architectural structure, rheological behaviour and functional stability of fine granules, given that their significance to the physicochemical features of the biomass catalysing the biological purification process. This review targets the EPS excretion from GS and introduces newly identified EPS components, EPS distribution in different granules, how to effectively extract and recover EPS from granules, key parameters affecting EPS production, and the potential applications of EPS-based biomaterials. GS-based EPS components are highly diverse and a series of new contents are highlighted. Due to high diversity, emerging extraction standards are proposed and recovery process is capturing particular attention. The major components of EPS are found to be polysaccharides and proteins, which manifest a larger diversity of relative abundance, structures, physical and chemical characteristics, leading to the possibility to sustainably recover raw materials. EPS-based biomaterials not only act as alternatives to synthetic polymers in several applications but also figure in innovative industrial/environmental applications, including gel-forming materials for paper industry, biosorbents, cement curing materials, and flame retardant materials. In the upcoming years, it is foreseen that productions of EPS-based biomaterials from renewable origins would make a significant contribution to the advancement of the circular economy.

SARS-CoV-2 from faeces to wastewater treatment: What do we know? A review.

SARS-CoV-2, the virus that causes COVID-19, has been found in the faeces of infected patients in numerous studies. Stool may remain positive for SARS-CoV-2, even when the respiratory tract becomes negative, and the interaction with the gastrointestinal tract poses a series of questions about wastewater and its treatments. This review aims to understand the viral load of SARS-CoV-2 in faeces and sewage and its fate in wastewater treatment plants (WWTPs). The viral load in the faeces of persons testing positive for SARS-CoV-2 was estimated at between 5·103 to 107.6 copies/mL, depending on the infection course. In the sewerage, faeces undergo dilution and viral load decreases considerably in the wastewater entering a WWTP with a range from 2 copies/100 mL to 3·103 copies/mL, depending on the level of the epidemic. Monitoring of SARS-CoV-2 in sewage, although no evidence of COVID-19 transmission has been found via this route, could be advantageously exploited as an early warning of outbreaks. Preliminary studies on WBE seem promising; but high uncertainty of viral loads in wastewater and faeces remains, and further research is needed. The detection of SARS-CoV-2 in sewage, based on RNA sequences and RT-PCR, requires a shared approach on sample pre-treatment and on-site collection to ensure comparable results. The finding of viral RNA in stools does not imply that the virus is viable and infectious. Viability of CoVs such as SARS-CoV-2 decreases in wastewater - due to temperature, pH, solids, micropollutants - but high inactivation in WWTPs can be obtained only by using disinfection (free chlorine, UVC light). A reduction in the quantity of disinfectants can be obtained by implementing Membrane-Bioreactors with ultrafiltration to separate SARS-CoV-2 virions with a size of 60-140 nm. In sludge treatment, thermophilic digestion is effective, based on the general consensus that CoVs are highly sensitive to increased temperatures.

Hydrogels formed by anammox extracellular polymeric substances: structural and mechanical insights.

The recovery of biopolymers from the waste sludge produced in wastewater treatments and their application in other industrial sectors, would substantially increase the environmental and economical sustainability of the process, promoting the development of a circular economy. In this study, extracellular polymeric substances (EPS) extracted from anammox granular waste sludge, were investigated and characterized. Rheological and differential scanning calorimetry measurements on EPS aqueous dispersions indicate the formation of an extended 3-D network above a threshold concentration, with a clear dependence of the mechanical and water retention properties on EPS content. The structural characterization, performed with transmission electron microscopy and small angle X-ray scattering, reveals the presence of functional amyloids as putative structural units, observed for the first time in an EPS-based hydrogel. As a proof of concept of the applicative potential, we explored the water and grease resistance provided to paper by an EPS coating. These results shed light on the structural details of EPS-based hydrogels, and pave the way for the possible use of EPS-based materials as a cheap, eco-friendly alternative to commonly adopted paper coatings, in line with a circular economy pattern for wastewater treatment.

Extraction, recovery and characterization of structural extracellular polymeric substances from anammox granular sludge.

The composition and colloidal properties of extracellular polymeric substances (EPS) from anammox granular sludge were investigated through a complete set of spectroscopic and scattering techniques. To fully characterize EPS, we developed a robust and reproducible extraction/recovery protocol specific for anammox biofilms, based on the change of water affinity under alternated alkaline and acidic conditions, each monitored with Z-potential and dynamic light scattering analysis. This method enabled both extraction as a colloidal suspension and recovery as a solid of large amounts of EPS (0.38 ±â€¯0.04 and 0.21 ±â€¯0.02 g/g, respectively), including for the first time its structural components. The dominance of the proteinaceous fraction was revealed by all methods tested, resulting in the highest protein/carbohydrates ratio reported for biofilms applied in the wastewater sector. The abundance of proteinaceous ordered structures and in particular of cross-ß motifs was detected, indicating for the first time the presence of amyloid-like aggregates in anammox EPS, and suggesting the key role of the protein fraction in determining the mechanical properties of the parent biofilm. The robustness and reproducibility of the proposed method fill the current gap towards a reliable full-scale recovery as well as towards an accurate and meaningful investigation of anammox EPS and pave the way for further exploration of their applicative potential thus stimulating the desirable shift from the current wastewater treatment perspective towards biorefinery in a circular economy context.

Comparative performance of enzymatic and combined alkaline-enzymatic pretreatments on methane production from ensiled sorghum forage.

This study investigated the effect of enzymatic and combined alkaline-enzymatic pretreatments on chemical composition and methane production from ensiled sorghum forage. Four commercial enzymatic preparations were tested and the two yielding the highest sugars release were added to evaluate any hydrolytic effect on both untreated and alkaline pretreated samples. In the combined alkaline-enzymatic pretreatment trials, the highest sugar release was found with Primafast and BGL preparations (added at a final concentration 0.12 and 0.20 mL/g TS, respectively), with a total monomeric content of 12 and 6.5 g/L. Fibre composition analysis confirmed that the combined alkaline-enzymatic pretreatment led to cellulose (up to 32 %) and hemicelluloses (up to 56 %) solubilisation, compared to the enzymatic pretreatment alone. BMP tests were performed on both untreated and pretreated samples, and time courses of methane production were fitted. Both enzymatic and combined alkaline-enzymatic pretreatment led to a methane production increase (304 and 362 mL CH4/g VS), compared to that of untreated sorghum (265 mL CH4/g VS), as  +15 and  +37 %, respectively. Moreover, higher specific methane production rates, compared to that of untreated sorghum (20.31 mL CH4/g VS/d), were obtained by applying the enzymatic and combined alkaline-enzymatic pretreatment (33.94 and 31.65 mL CH4/g VS/d), respectively.

Maize mono-digestion efficiency: results from laboratory tests.

A laboratory experimental campaign was carried out in order to assess the optimal configuration for the anaerobic digestion of a mixture of sweet corn and ensiled maize. Batch hydrolysis tests were conducted at 35 and 55 °C and at four different particle sizes (2, 5, 20 and 50 mm) obtained by manual chopping and sieving. Chemical pre-treatment by 24 h incubation at various acid and alkaline pH was also considered for its potential to increase the maize methane yield. Results suggest that the hydrolytic phase proceeds significantly faster under thermophilic conditions. Significant differences in the solubilization rate were also observed when comparing coarse (20-50 mm) with fine (2-5 mm) particles, while 2 and 5 mm particles were solubilized at similar rates. No advantages from the chemical pre-treatment, in terms of solubilization efficiency and biomethanization potential were observed. According to these preliminary results, a two-stage semi-continuous laboratory plant consisting of a thermophilic hydrolytic reactor followed by a mesophilic methanogenic reactor was operated for 110 days. Steady state loading parameters were: influent concentration (maize mixture diluted in tap water) of 46 g VS/L, hydraulic retention time of 31 d, organic loading rate of 1.5 g VS/L/d. Alkalinity was dosed to the methanogenic reactor to avoid pH drops. Collected data allowed the average biodegradation efficiency to be estimated at around 60-65%.

Fate of surfactants in membrane bioreactors and conventional activated sludge plants.

Two membrane bioreactors (MBRs) were operated at high sludge retention time (SRT) (between 30 and 75 d) in parallel to a conventional activated sludge plant (CASP) conducted at SRT = 10 d. The fate of linear alkylbenzene sulfonate (LAS), nonylphenol ethoxylates (NP(n)EO, n = 1-15), nonylphenoxy carboxylates (NP(n)EC, n = 1-2), and nonylphenol (NP) in these systems was investigated. All systems were very efficient in the removal of LAS (around 99%). The analysis of variance showed that the difference in the removal efficiency of LAS in the CASP and the MBR operated at SRT = 65-75 d (respectively 99.0 ± 0.43 and 99.8 ± 0.11) were significant (p < 0.05), confirming the importance of SRT in the removal of LAS. Comparison between the CASP and the MBRs in the removal efficiency of nonylphenolic compounds were conducted considering NP(3-15)EO, the sum of NP(1-15)EO, NP(1-2)EC, and nonylphenol (NP). In all cases MBRs were more efficient than the CASP. In the case of NP the removal was about 76 ± 7.5% for the CASP and 90% ± 12.1 and 82 ± 8.7% for the MBRs. Better performance of MBRs in the removal of nonylphenolic compounds can be attributed to a better degradation. For example, if the sum of NP(1-15)EO and NP(1-2)EC is considered, estimated biodegradation was about 48% for the CASP and 72% for MBRs.

Environmental occurrence and degradation of the herbicide n-chloridazon.

A sampling campaign was carried out for n-chloridazon (n-CLZ) and its degradation product desphenyl-chloridazon (DPC) in the Hesse region (Germany) during the year 2007: a total of 548 environmental samples including groundwater, surface water and wastewater treatment plant (WWTP) effluent were analysed. Furthermore, aerobic degradation of n-CLZ has been studied utilising a fixed bed bioreactor (FBBR). In surface water, n-CLZ was detected at low concentrations (average 0.01+/-0.06mugL(-1); maximum 0.89mugL(-1)) with a seasonal peak, whereas DPC was present throughout the year at much higher concentrations (average 0.72+/-0.81mugL(-1); maximum 7.4mugL(-1)). Higher n-CLZ concentrations were observed in the North compared with South Hesse, which is ascribed to a higher density of agricultural areas. Furthermore, methylated DPC (Me-DPC), another degradation product, was detected in surface water. In the degradation test, n-CLZ was completely converted to DPC at all concentrations tested (Me-DPC was not formed under the test conditions). DPC was resistant to further degradation during the whole experimental period of 98 days. The results obtained suggest persistence and high dispersion of DPC in the aquatic environment.