Complex waste streams, such as sludge reject water from anaerobic digestion, often contain a multitude of cations at varying concentrations, with the ammonium ion (NH₄⁺) typically being the most abundant. Recently, electrodialysis (ED) has been developed as a technology for the removal and recovery of NH₄⁺ from reject water. However, the further development of ED for targeting NH₄⁺ recovery faces lack of reliable performance prediction and standardized operating strategies due to cation competition. It is postulated that selective rejection of divalent cations can be achieved through the use of monovalent-selective cation-exchange membranes (mCEMs). Due to their higher electrical resistance, questions remain regarding the cationic compositions under which mCEMs provide a substantial performance benefit. In the present study, three feed solutions simulating different molar cation compositions of reject water were subjected to ED using both mCEMs and conventional cation-exchange membranes (CEMs). The feed solutions were categorized based on the molar fraction of NH₄⁺ relative to the total cation content. Results showed that the perm-selectivity of NH₄⁺ over Mg²⁺ and Ca²⁺ was enhanced when using mCEMs. Moreover, mCEMs resulted in a higher overall NH₄⁺ removal efficiency compared to standard CEMs. At a relatively low NH₄⁺ molar fraction (0.32), mCEMs outperformed CEMs in terms of current efficiency. Notably, at an intermediate molar fraction (0.58), energy consumption was lower for mCEMs compared to CEMs, but only up to a critical degree of desalination (CDD). At a high molar fraction (0.89), the contribution of mCEMs was insignificant compared to that of CEMs. The CDD was identified as a pragmatic operational parameter beyond which further desalination leads to disproportionate energy penalties. For on-site-process-control of NH₄⁺ removal with ED, the CDD demonstrated that membrane selection and operating thresholds are strongly dependent on reject water composition.

Biogas, generated from small scale digesters, is a traditional energy source for satisfying the thermal energy demand in off-grid communities. Recent developments in small scale solid oxide fuel cells (SOFCs) technology and progress in research and development of dry reforming, opens perspectives to couple small scale SOFCs with already existing digesters to meet both thermal and electrical energy demand, enabling power access to off-grid communities. However, one of the major challenges for SOFC integration to small scale digesters is the effect of biogas impurities, such as H₂S, on the performance of SOFCs. Previous work has shown that local operational practices could influence the biogas quality and particularly the H₂S content in the biogas. The here presented research expanded on the use of cow urine instead of water as solvent in manure digestion as a potential operational strategy that enables in-situ reduction of H₂S in the evolving biogas. This research investigated the following hypotheses: 1) urine addition results in a high pH that favours HS⁻ over H₂S, 2) given the presence of metal elements in the cow urine, insoluble metal sulphides are being formed, reducing the biogas H₂S content. The research was carried out by measuring cow urine composition of various samples, assessing the effects of different urine/water/manure mixtures on the evolving biogas-H₂S concentration, and verifying the experimental findings with phreeqC equilibrium speciation. Bio-kinetic modelling, using the anaerobic digestion model nr 1 (ADM1), was subsequently performed to explore the influence of different feed compositions on the H₂S content in the biogas. It was observed that addition of cow urine in all experiments resulted in an elevated pH of the reactor compared to water dilution, yet both experiments I and II-2 showed an increased maximum H₂S content when urine dilution was applied, compared to water dilution. Cow urine and cow dung characterisation in terms of metals and S, showed that experiment II-1 had the highest Fe:S ratio of 1:0.3–1:0.9. Equilibrium modelling confirmed that despite the positive urine-induced pH effect, the measured Fe:S ratios could indeed be decisive, as with an Fe;S ratio of 1:6 and 1:0.5, the H₂S production at equilibrium was 61 and 10 mL/ kg of solution, respectively. Furthermore, it was predicted through bio-kinetic modelling that inconsistency in feedstock composition may result in temporary H₂S peaks exceeding 400 ppm. Overall, results showed that if a cow urine/manure mixture is characterised by a total metal:S ratio exceeding 1:0.5 and total S content of less than 0.5 mM, then hydrolysed cow urine addition presents an interesting in-situ H₂S cleaning strategy for biogas-SOFC applications.

Purpose of Review: Liquid crystal monomers (LCMs), used extensively in liquid crystal displays (LCDs), have emerged as persistent, bioaccumulative, and toxic organic pollutants. A network analysis of SCOPUS data revealed significant knowledge gaps, especially concerning the fate of LCMs in WWTPs. The available literature highlights that influent LCM concentrations vary widely, with elevated levels linked to industrial and e-waste recycling activities. This review examines the occurrence, fate, and treatment of LCMs, particularly fluorinated LCMs (F-LCMs), in wastewater treatment plants (WWTPs). Recent Findings: Conventional WWTP processes achieve moderate removal efficiencies (~ 84%) for LCMs, but F-LCMs often persist. Advanced treatment techniques such as UV/peroxydisulfate (UV/PDS) showed removal rates of 77–84% for LCMs with biphenyl and ethoxy groups. These groups alter electron distribution, making the molecules more susceptible to oxidative attack by reactive species such as hydroxyl and sulfate radicals. Degradation pathways include cleavage of biphenyl, ethoxy, and C-F bonds, producing less toxic by-products such as oxalic acid and cyclohexane. However, some degradation intermediates formed are toxic, necessitating further research of the treatment processes. Summary: This review underscores the need for systematic monitoring of LCMs in wastewater and their transformation products in treated wastewater and sludge, alongside advancements in treatment technologies to mitigate environmental and health risks. This review highlights the urgency of improving wastewater management strategies for LCMs and the need for future research to address the critical knowledge gaps.

The anaerobic degradation of phenolic compounds presents substantial challenges due to their toxicity to methanogenic biomass and inherently low conversion rates. Recent studies indicate that nano-magnetite can stimulate direct interspecies electron transfer (DIET), potentially enhancing phenol conversion and methane production. This study employed two anaerobic membrane bioreactors (AnMBRs) to investigate phenol and p-cresol degradation under stepwise increasing loading rates, with complete retention of biomass in both reactors. While AnMBR-C served as a control, nano-magnetite was additionally supplemented to reactor AnMBR-M at a concentration of 40 mmol/L in Phase 1 and 20 mmol/L in Phase 2. Results demonstrated that AnMBR-M supplemented with 20 mmol/L nano-magnetite tolerated higher phenolic loading rates compared to AnMBR-C. In Phase 2, a higher total Fe concentration was observed in AnMBR-M, suggesting an enhanced electron transfer mechanism via dissimilatory iron reduction-oxidation cycle. Follow-up batch experiments revealed that magnetite-adapted biomass had more tolerance to phenol inhibition. A 16S-rRNA sequencing was conducted to characterize microbial communities within both reactors. Results suggested that DIET was stimulated in Phase 1, as shown by the enrichment of the electrogenic Pseudomonas and Methanolinea in AnMBR-M. However, the possibly stimulated DIET in Phase 1 could not alleviate the inhibition caused by excessive 40 mmol/L nano-magnetite dosage. Notably, there was no significant difference between the genera of AnMBR-C and AnMBR-M by the end of Phase 2. However, short-chain fatty acid degrader Mesotoga was more enriched in AnMBR-M. Moreover, species-level analysis showed that AnMBR-M had a sixfold higher relative abundance of Methanosaeta harundinacea compared to AnMBR-C.

Recent research showed that the recovery of ammonia from simulated ammonium citrate scrubber effluent via bipolar membrane electrodialysis (BPMED) is less energy-intensive than from ammonium sulfate solutions. Nonetheless, the application of citric acid as scrubbing agent is limited by its high costs. This study aimed to improve BPMED performance for ammonium recovery using ammonium salts mixtures (ammonium sulfate and ammonium citrate) as feed solutions. Unlike previous studies that focused mainly on single-salt systems, it investigated how this combination affects ammonium recovery efficiency, current efficiency, energy consumption, ammonia diffusion, H⁺ and OH⁻ leakage to the diluate compartment, and anions transport across anion exchange membranes (AEMs) during BPMED. The ammonium recovery efficiency was higher for pure ammonium citrate (45.2 %) and mixture solutions (32.0–45.9 %) than for pure ammonium sulfate (26.8 %). Higher efficiency resulted from reduced competition between protons and ammonium across the cation exchange membrane (CEM). Feed with a higher ammonium citrate proportion increased buffer capacity, preventing protons leakage from the acid to the diluate compartment. This resulted in higher ammonium current efficiency for pure ammonium citrate (34.8 %) and mixture solutions (24.9–35.7 %) than for pure ammonium sulfate (20.4 %). The energy consumption was lower for pure ammonium citrate (14.1 kWh/kg-N recovered) and mixture solutions (13.0–17.4 kWh/kg-N recovered), than for pure ammonium sulfate (22.3 kWh/kg-N recovered). Ammonia diffusion from the base to the acid compartment reduced current efficiency by 19–23 % and accounted for 30–40 % of the total ammonium transported from the feed. This study demonstrated the effective use of ammonium citrate as one of the salts in the mixture to achieve high ammonium recovery efficiency with reduced energy consumption.

In this study, we investigated the use of BiVO₄/TiO₂-GO heterojunction photoanode in a PEC based AOP to simultaneously remove four organic micropollutants (OMPs): benzotriazole (BTA), carbamazepine (CBZ), caffeine (CAF) and diclofenac (DIC) from demineralized water. Each OMP had an initial concentration of 40 µg L⁻¹. Ultrasonic spray pyrolysis (USP) was used to deposit BiVO₄ and TiO₂-GO layers on fluorine doped tin oxide (FTO) electrodes. The heterojunction photoanode at an applied voltage of 1 V (vs Ag/AgCl) achieved simultaneous removal efficiencies of 100 % for DIC, 54 % for CBZ, 36 % for BTA and 33 % for BTA under simulated solar light. Compared to the pristine BiVO₄ photoanode, the heterojunction photoanode showed 50 % higher removal efficiency for BTA, CBZ and CAF. The reaction kinetics revealed that the first order rate coefficient for DIC removal was about nine times higher than that of CBZ and fifteen times higher than those of BTA and CAF. To assess scalability, a computational fluid dynamics (CFD) model incorporating the experimentally determined reaction kinetics was developed for a conceptually designed up-scaled PEC reactor. The model analyzed the effect of reactor design and fluid flow conditions on the removal of OMPs. Under turbulent flow conditions, enhanced removal efficiency was observed for all four OMPs, which was attributed to the effects of eddy diffusion and convective mixing. The optimized reactor design under turbulent flow condition achieved an 80 % removal efficiency for all four OMPs within 25 min under a light intensity of 400 W m⁻². The findings highlight the potential of BiVO₄/TiO₂-GO heterojunction photoanodes for efficient and scalable PEC water treatment, showing a promising approach for the elimination of OMPs from wastewater.

Despite growing scientific interest in the past decade, bipolar membrane electrodialysis has seen limited advancement in controlled operation of water dissociation via the bipolar membrane (BPM). For nutrient recovery applications, such as ammonia (NH₃) extraction from anaerobic digestion reject water, implementing in-situ pH control in the base solution could enhance energy efficiency. By controlling the electric current, pH is regulated through OH⁻ generation from the bipolar membrane (BPM). Once the targeted pH is reached, the electric current is applied in pulses and pauses with the purpose to sustain and to not overpass the pH setpoint. A selective electrodialysis reversal (SEDR) combined with a two-compartment bipolar membrane electrodialysis (BPMC) and vacuum membrane stripping (VMS) enabled the recovery and conversion of ammonium ions (NH₄⁺) into volatile ammonia (NH₃). Operating the BPMC with the developed pH control method lowered energy consumption (E_NH4⁺) and improved current efficiency for NH₄⁺ removal compared to constant current (CC) operation. Under pH control, the BPMC maintained the target pH throughout the whole operation, with an E_NH4⁺ between 12.5 and 35.3 MJ·kgN⁻¹, compared to 12.1 and 78.6 MJ·kgN⁻¹ under CC. The current efficiency was maintained across setpoints with pH control, ranging between 25 % and 29 %. With CC, the current efficiency declined from 27 % to 12 % at higher current densities. Furthermore, pH control applying a pulsed electric current reduced the occurrence of scaling by minimising the transport of divalent cations across the cation exchange membrane and CO₂ formation in the acid compartment. Similar removal efficiencies were attained, applying pH controlled operation and CC; however, both methods performed a declining removal efficiency during 30 h operation. The developed pH control method can provide distinct improvement in scale-up applications, where energy reduction by preventing excessive water dissociation by the BPM is of interest. In addition, external caustic dosing can be substituted by pH control with a BPMC layout of the stack, reducing the residual impurities of the chemical dosing.

Abstract: Presence of carbohydrates hampers protein degradation in anaerobic digesters. To understand this phenomenon, we used proteogenomics to identify the active protein-degraders in the presence of low and high carbohydrates concentrations. Active metabolic pathways of the identified protein-degraders were investigated using proteomics with ¹³C-protein substrates (protein stable isotope probing). Results showed that 1) Acinetobacter was the active protein-degraders under both protein-fed and protein-glucose mixture-fed conditions, 2) the relative abundance of Acinetobacter was not affected by the presence of carbohydrates, 3) the incorporation of the ¹³C-labelled protein substrate was predominantly observed in outer membrane-bound proteins and porin proteins, which are associated with proteinases or the transportation of amino acids across the cell wall. The Acinetobacter metabolic model and the incubation conditions suggested that glucose and proteins were degraded through anaerobic respiration. The negative impact of carbohydrates on protein biodegradation was attributed to Acinetobacter's preference for carbohydrates. This work highlights that efficient degradation of protein and carbohydrate mixtures in anaerobic digesters requires a staged or time-phased approach and enrichment of active protein-degraders, offering a new direction for process optimization in anaerobic digestion systems.

This mini review explores the potential of visible light–driven bismuth vanadate (BiVO₄)-based photoanodes for removing trace organic pollutants from water. It highlights the advantages of using BiVO₄-based photoanodes over conventional UV-driven photoanodes in water treatment. The mechanism of reactive species generation through water oxidation is discussed. The review also highlights the role of sulfate and sulfite radicals in enhancing pollutant degradation. Furthermore, it evaluates how heterojunction formation improves the removal efficiency of BiVO₄-based photoanodes by reducing charge carrier recombination. Limited research on BiVO₄-based photoanodes for the simultaneous removal of multiple organic pollutants at low concentrations (<1 mg L⁻¹) from real wastewater is identified as a key knowledge gap. Addressing this gap could advance the application of BiVO₄-based photoanodes in photoelectrocatalytic-based advanced oxidation processes.

The removal of ammonium and ammonia, represented as total ammoniacal nitrogen (TAN), from reject water through electro-dialysis (ED) and bipolar membrane electrodialysis (BPMED) encounters challenges such as organic fouling, NH₃ back-diffusion, and high energy consumption. The efficacy of electrodialysis reversal (EDR) combined with bipolar membrane electrodialysis using cation-exchange membranes (BPC) was assessed as a more practical configuration (EDR + BPC). Additionally, a novel configuration involving monovalent selective cation-exchange membranes (MSCEMs) in an EDR + BPC setup (SEDR + BPC) was investigated. Comparisons were made among BPMED, EDR + BPC, and SEDR + BPC under three load ratios (L_N) of 0.8, 1, and 1.3 during continuous operation. The innovative SEDR + BPC configuration, with an L_N of 0.8, exhibited the lowest energy consumption for transported TAN (E_TAN) at 4.4 MJ·kgN⁻¹ removal and achieved the highest TAN removal efficiency of 78 % with an L_N of 1.3. In contrast to conventional BPMED, SEDR + BPC allowed for the recovery of potentially back-diffused NH₃ into the acid chamber, minimizing transport losses. Furthermore, scaling in the base chamber was reduced due to the contribution of MSCEMs when applying an L_N of 0.8. The MSCEMs increased the molar ratio of TAN over (Mg²⁺ + Ca²⁺) in the concentrate and decreased it in the diluate. EDR + BPC and SEDR + BPC configurations exhibited stable and lower cell resistance throughout the operation compared to BPMED, attributed to their ability to generate higher concentration gradients. The results clearly demonstrated the feasibility of low-energy TAN removal from real reject water from sludge anaerobic digestion using the SEDR + BPC setup.

While air stripping combined with acid scrubbing remains a competitive technology for the removal and recovery of ammonia from wastewater streams, its use of strong acids is concerning. Organic acids offer promising alternatives to strong acids like sulphuric acid, but their application remains limited due to high cost. This study proposes an integration of air stripping and organic acid scrubbing with bipolar membrane electrodialysis (BPMED) to regenerate the organic acids. We compared the energy consumption and current efficiency of BPMED in recovering dissolved ammonia and regenerating sulphuric, citric, and maleic acids from synthetic scrubber effluents. Current efficiency was lower when regenerating sulphuric acid (22 %) compared to citric (47 %) and maleic acid (37 %), attributable to the competitive proton transport over ammonium across the cation exchange membrane. Organic salts functioned as buffers, reducing the concentration of free protons, resulting in higher ammonium removal efficiencies with citrate (75 %) and malate (68 %), compared to sulphate (29 %). Consequently, the energy consumption of the BPMED decreased by 54 % and 35 % while regenerating citric and maleic acids, respectively, compared to sulfuric acid. Membrane characterisation experiments showed that the electrical conductivity ranking, ammonium citrate > ammonium malate > ammonium sulphate, was mirrored by the energy consumption (kWh/kg-N recovered) ranking, ammonium sulphate (15.6) < ammonium malate (10.2) < ammonium citrate (7.2), while the permselectivity ranking, ammonium sulphate > ammonium citrate > ammonium malate, aligned with calculated charge densities. This work demonstrates the potential of combining organic acid scrubbers with BPMED for ammonium recovery from wastewater effluents with minimum chemical input.

Structural extracellular polymeric substances (SEPS) as valuable biopolymers, can be extracted from waste activated sludge (WAS). However, the extraction yield is typically low, and detailed information on SEPS characterizations, as well as proper treatment of the sludge after SEPS extraction, remains limited. This study aimed to optimize the conditions of heating-Na₂CO₃ extraction process to increase the yield of SEPS extracted from WAS. Subsequently, SEPS were characterized, and, for the first time, insights into their protein composition were uncovered by using proteomics. A maximum SEPS yield of 209 mg g^-1 volatile solid (VS) was obtained under optimal conditions: temperature of 90 °C, heating time of 60 min, Na⁺ dosage of 8.0 mmol/g VS, and pH required to precipitation of 4.0, which was comparable to that from the aerobic granular sludge reported in literature. Proteomics analysis unveiled that the proteins in SEPS primarily originated from microorganisms involved in nitrogen fixation and organic matter degradation, including their intracellular and membrane-associated regions. These proteins exhibited various catalytic activities and played crucial roles in aggregation processes. Besides, the process of SEPS extraction significantly enhanced volatile fatty acid (VFA) production during the anaerobic fermentation of residual WAS after SEPS extraction. A maximum VFA yield of 420 ± 14 mg COD/g VS_added was observed in anaerobic fermentation of 10 d, which was 77.2 ± 0.1 % higher than that from raw sludge. Mechanism analysis revealed that SEPS extraction not only improved WAS disintegration and solubilization but also reduced the relative activity of methanogens during anaerobic fermentation. Moreover, SEPS extraction shifted the microbial population during anaerobic fermentation in the direction towards hydrolysis and acidification such as Fermentimonas sp. and Soehngenia sp. This study proposed a novel strategy based on SEPS extraction and VFA production for sludge treatment, offering potential benefits for resource recovery and improved process efficiency.

Simulated ammonium sulfate scrubber effluent was treated using bipolar membrane electrodialysis (BPMED) to recover sulfuric acid for reuse in the scrubber, and ammonium hydroxide as a product, without using any chemicals. The effect of pH and temperature of the feed solution on the energy consumption of the BPMED and the purity of the recovered acid and base were investigated in batch experiments. Experiments were conducted during a 3-hour period using a scrubber effluent with the following characteristics: 50 g/L ammonium sulfate, pH ranging from 1 to 5 and temperature ranging from 20 °C to 30 °C. The energy consumption at pH 5 was lower than that at pH 1, i.e., 6.9 MJ/kg SO₄^2- and 7.7 MJ/kg SO₄^2-, respectively. The purity of the acid recovered from the feed solution with a pH of 5 was 36 %, whereas the feed with a pH of 1 resulted in an acid purity of 72 %. These values corresponded to a mass of ammonia diffusion of 6.9 g and 2.3 g, respectively. The purity of the base recovered from the feed with a pH of 5 was 84 %, whereas this was 69 % for the feed with a pH of 1. Higher temperature of the feed solution, i.e., 30 °C compared to 20 °C, resulted in a lower energy consumption: 7.1 MJ/kg SO₄^2- compared to 9.5 MJ/kg SO₄²⁻, respectively. The temperature had a very limited effect on the acid and base purities, with values ranging from 80 % to 82 % for the acid, and from 33 % to 36 % for the base. Our study demonstrated the effective application of BPMED for the treatment of simulated acidic scrubber effluent, with simultaneous recovery of ammonia and sulfuric acid.

Treating protein-rich wastewater using cost-effective and simple-structured single-stage reactors presents several challenges. In this study, we applied an anaerobic sequencing batch reactor (AnSBR) to treat protein-rich wastewater from a slaughterhouse. We focused on identifying the key factors influencing the removal of chemical oxygen demand (COD) and the settling performance of the sludge. The AnSBR achieved a maximum total COD removal of 90%, a protein degradation efficiency exceeding 80%, and a COD to methane conversion efficiency of over 70% at organic loading rates of up to 6.2 g COD L⁻¹ d⁻¹. We found that the variations in both the organic loading rate within the reactor and the hydraulic retention time in the buffer tank had a significant effect on COD removal. The hydraulic retention time in the buffer tank and the reactor, which determined the ammonification efficiencies and the residual carbohydrate concentrations in the reactor liquid, affected the sludge settleability. Furthermore, the genus Clostridium sensu stricto 1, known as protein- and lipids-degraders, was predominant in the reactor. Statistical analysis showed a significant correlation between the core microbiome and ammonification efficiency, highlighting the importance of protein degradation as the governing process in the treatment. Our results will provide valuable insights to optimise the design and operation of AnSBR for efficient treatment of protein-rich wastewater.

Bovine serum albumin (BSA) and casein (CAS) were used in batch tests to compare the protein degradation in the presence and absence of carbohydrates and volatile fatty acids (VFAs). The modified Gompertz model was applied to estimate reaction rates. The results showed that deamination was the rate-limiting step, with a rate ranging between 2.7 and 12.7 mgN·h⁻¹. Higher protein structural complexity negatively affected protein hydrolysis, deamination, and methanogenesis by a factor of 1.6–3.8; whereas a higher protein concentration improved the conversion rates. A carbohydrate:protein COD ratio of 1 improved the hydrolysis rate of BSA from 26 mg·h⁻¹ to 45 mg·h⁻¹, and that of CAS from 98 mg·h⁻¹ to 157 mg·h⁻¹; whereas the deamination rate slightly decreased from 2.7 mg N·h⁻¹ to 2.5 mg N·h⁻¹ and from 6.0 mg N·h⁻¹ to 5.6 mg N·h⁻¹. Additionally, an initial VFAs:protein COD ratio of 1 decreased the CAS deamination rate by 17 %.

Bitumen fume condensate (BFC) is a hazardous wastewater generated at asphalt reclamation and production sites. BFC contains a wide variety of potentially toxic organic pollutants that negatively affect anaerobic processes. In this study, we chemically characterized BFC produced at an industrial site and evaluated its degradation under anaerobic conditions. Analyses identified about 900 compounds including acetate, polycyclic aromatic hydrocarbons, phenolic compounds, and metal ions. We estimated the half maximal inhibitory concentrations (IC₅₀) of methanogenesis of 120, 224, and 990 mgCOD·L⁻¹ for three types of anaerobic biomass, which indicated the enrichment and adaptation potentials of methanogenic biomass to the wastewater constituents. We operated an AnMBR (7.0 L, 35 °C) for 188 days with a mixture of BFC, phenol, acetate, and nutrients. The reactor showed a maximum average COD removal efficiency of 87.7 ± 7.0 %, that corresponded to an organic conversion rate of 286 ± 71 mgCOD⁻¹·L⁻¹d⁻¹. The microbial characterization of the reactor's biomass showed the acetoclastic methanogen Methanosaeta as the most abundant microorganism (43 %), whereas the aromatic and phenol degrader Syntrophorhabdus was continuously present with abundances up to 11.5 %. The obtained results offer the possibility for the application of AnMBRs for the treatment of BFC or other petrochemical wastewater.