Enhancing selective ammonium transport in membrane electrochemical systems.

Recovering ammonia nitrogen from wastewater is a sustainable strategy that simultaneously addresses both nitrogen removal and fertilizer production. Membrane electrochemical system (MES), which utilizes electrochemical redox reactions to transport ammonium ions through cation exchange membranes, has been considered as an effective technology for ammonia recovery from wastewater. In this study, we develop a mathematical model to systematically investigate the impact of co-existing ions on the transport of ammonium (NH4+) ions in MES. Our analysis elucidates the importance of pH values on both the NH4+ transport and inert ion (Na+) transport. We further comprehensively assess the system performance by varying the concentration of Na+ in the system. We find that while the inert cation in the initial anode compartment competes with NH4+ transport, NH4+ dominates the cation transport in most cases. The transport number of Na+ surpasses NH4+ only if the fraction of Na+ to total cation is extremely high (>88.5%). Importantly, introducing Na+ ions into the cathode compartment significantly enhances the ammonia transport due to the Donnan dialysis. The analysis of selective ion transport provides valuable insights into optimizing both selectivity and efficiency in ammonia recovery from wastewater.

Bioelectrochemically-assisted ammonia recovery from dairy manure.

The sustainability of direct land application of dairy manure is challenged by significant nutrient losses. Bioelectrochemical systems for ammonia recovery offer a manure management strategy that can recover both ammoniacal and organic nitrogen as a stable ammonia fertilizer. In this research, a microbial fuel cell (MFC) was used to treat two types of dairy manure under a variety of imposed anode compartment conditions. The system achieved a maximum coulombic efficiency of 20 ± 18 % and exhibited both COD and total nitrogen removals of approximately 60 %. Furthermore, the MFC showed a maximum organic nitrogen removal of 73.8 ± 12.1 %, and no differences in organic nitrogen (orgN) removal were detected among different conditions tested. Decreasing concentrations of anolyte ammonia nitrogen coupled with the observed orgN removal from the anolyte indicate that the MFC is effective at recovering orgN in dairy manure as ammoniacal nitrogen in the catholyte. Additionally, ion competition between NH4+ and other relevant cations (Na+, K+, and Mg2+) for transport across the CEM was investigated, with only K+ showing minor competitive effects. Based on the results of this research, we propose three key processes and two sub-processes that contribute to the successful operation of the MFC for nitrogen recovery from dairy manure. Bioelectrochemical systems for nitrogen recovery from dairy manure offer a novel, robust technology for producing a valuable ammonia nitrogen fertilizer, a thus far untapped resource in dairy manure streams.

Ammonia recovery from organic nitrogen in synthetic dairy manure with a microbial fuel cell.

Increasing pressures on the animal and cropland agriculture sectors have led to the realization of problems with animal waste management and ammonia-based fertilizer supply. Bioelectrochemical systems (BES) are a new-age technology that offer a way to address these problems. Microbial fuel cells (MFCs), one type of BES, are traditionally used for electricity generation from microbial degradation of organic matters, but can also be used to recover nutrients from wastes simultaneous with treatment. This research investigated an MFC for ammonia recovery from the organic nitrogen (orgN) fraction of synthetic dairy manure, using the simple amino acid glycine as the orgN source. We used five different synthetic manure compositions to determine their effects on MFC performance, and found minimal sacrifices in performance under orgN conditions when compared to the base condition without orgN. The MFC achieved greater than 90% COD removal in all orgN conditions. Nitrogen (N) removal efficiencies of between 40% and 60% were achieved in orgN conditions, indicating that organic nitrogen can be used as the substrate for ammonia mineralization and further recovery as fertilizer. In addition, we found the MFC was largely populated by electrogenic organisms from the phyla Bacteroidota, Firmicutes, Proteobacteria, and Halobacterota, with organisms in both Bacteroidota and Firmicutes capable of N mineralization present. Lastly, we found that in conditions where orgN is scarce and the only N source provided, microbes preferentially degraded organic matter from other dead organisms, especially as an N source. This increases the concentration of N in the MFC system and introduces important operational constraints for MFCs operated for ammonia recovery from orgN.

The Application of Cation Exchange Membranes in Electrochemical Systems for Ammonia Recovery from Wastewater.

Electrochemical processes are considered promising technologies for ammonia recovery from wastewater. In electrochemical processes, cation exchange membrane (CEM), which is applied to separate compartments, plays a crucial role in the separation of ammonium nitrogen from wastewater. Here we provide a comprehensive review on the application of CEM in electrochemical systems for ammonia recovery from wastewater. Four kinds of electrochemical systems, including bioelectrochemical systems, electrochemical stripping, membrane electrosorption, and electrodialysis, are introduced. Then we discuss the role CEM plays in these processes for ammonia recovery from wastewater. In addition, we highlight the key performance metrics related to ammonia recovery and properties of CEM membrane. The limitations and key challenges of using CEM for ammonia recovery are also identified and discussed.

Electrochemical-Osmotic Process for Simultaneous Recovery of Electric Energy, Water, and Metals from Wastewater.

A highly-efficient, autonomous electrochemical-osmotic system (EOS) is developed for simultaneous recovery of electric energy, water, and metals from wastewater. We demonstrate that the system can generate a maximum electric power density of 10.5 W m-2 using a spontaneous Fe/Cu2+ galvanic cell, while simultaneously achieving copper recovery from wastewater. With an osmotic pressure difference generated by the deployed electrochemical reactions, water is osmotically extracted from the feed solution with the EOS at a water flux of 5.1 L m-2 h-1. A scaled-up EOS realizes a power density of 105.8 W per m-3 of treated water to light an LED over 24 h while also enhancing water extraction and metal recovery. The modularized EOS obtains ultrahigh (>97.5%) Faradaic efficiencies under variable operating conditions, showing excellent system stability. The EOS is also versatile: it can recover Au, Ag, and Hg from wastewaters with simultaneous electricity and water coproduction. Our study demonstrates a promising pathway for realizing multiresource recycling from wastewater by coupling electrochemical and osmosis-driven processes.

Energy Efficiency of Electro-Driven Brackish Water Desalination: Electrodialysis Significantly Outperforms Membrane Capacitive Deionization.

Electro-driven technologies are viewed as a potential alternative to the current state-of-the-art technology, reverse osmosis, for the desalination of brackish waters. Capacitive deionization (CDI), based on the principle of electrosorption, has been intensively researched under the premise of being energy efficient. However, electrodialysis (ED), despite being a more mature electro-driven technology, has yet to be extensively compared to CDI in terms of energetic performance. In this study, we utilize Nernst-Planck based models for continuous flow ED and constant-current membrane capacitive deionization (MCDI) to systematically evaluate the energy consumption of the two processes. By ensuring equivalently sized ED and MCDI systems-in addition to using the same feed salinity, salt removal, water recovery, and productivity across the two technologies-energy consumption is appropriately compared. We find that ED consumes less energy (has higher energy efficiency) than MCDI for all investigated conditions. Notably, our results indicate that the performance gap between ED and MCDI is substantial for typical brackish water desalination conditions (e.g., 3 g L-1 feed salinity, 0.5 g L-1 product water, 80% water recovery, and 15 L m-2 h-1 productivity), with the energy efficiency of ED often exceeding 30% and being nearly an order of magnitude greater than MCDI. We provide further insights into the inherent limitations of each technology by comparing their respective components of energy consumption, and explain why MCDI is unable to attain the performance of ED, even with ideal and optimized operation.

Tackle reverse solute flux in forward osmosis towards sustainable water recovery: reduction and perspectives.

Forward osmosis (FO) has emerged as a potentially energy-efficient membrane treatment technology to yield high-quality reusable water from various wastewater/saline water sources. A key challenge remained to be solved for FO is reverse solute flux (RSF), which can cause issues like reduced concentration gradient and loss of draw solutes. Yet no universal parameters have been developed to compare RSF control performance among various studies, making it difficult to position us in this "battle" against RSF. In this paper, we have conducted a concise review of existing RSF reduction approaches, including operational strategies (e.g., pressure-, electrolysis-, and ultrasound-assisted osmosis) and advanced membrane development (e.g., new membrane fabrication and existing membrane modification). We have also analyzed the literature data to reveal the current status of RSF reduction. A new parameter, mitigation ratio (MR), was proposed and used together with specific RSF (SRSF) to evaluate RSF reduction performance. Potential research directions have been discussed to help with future RSF control. This review intends to shed more light on how to effectively tackle solute leakage towards a more cost-effective and environmental-friendly FO treatment process.

Effects of current generation and electrolyte pH on reverse salt flux across thin film composite membrane in osmotic microbial fuel cells.

Osmotic microbial fuel cells (OsMFCs) take advantages of synergy between forward osmosis (FO) and microbial fuel cells (MFCs) to accomplish wastewater treatment, current generation, and high-quality water extraction. As an FO based technology, OsMFCs also encounter reverse salt flux (RSF) that is the backward transport of salt ions across the FO membrane into the treated wastewater. This RSF can reduce water flux, contaminate the treated wastewater, and increase the operational expense, and thus must be properly addressed before any possible applications. In this study, we aimed to understand the effects of current generation and electrolyte pH on RSF in an OsMFC. It was found that electricity generation could greatly inhibit RSF, which decreased from 16.3 ± 2.8 to 3.9 ± 0.7 gMH when the total Coulomb production increased from 0 to 311 C. The OsMFC exhibited 45.9 ± 28.4% lower RSF at the catholyte pH of 3 than that at pH 11 when 40 Ω external resistance was connected. The amount of sodium ions transported across the FO membrane was 18.3-40.7% more than that of chloride ions. Ion transport was accomplished via diffusion and electrically-driven migration, and the theoretical analysis showed that the inhibited electrically-driven migration should be responsible for the reduced RSF. These findings are potentially important to control and reduce RSF in OsMFCs or other osmotic-driven processes.

Understanding Ammonium Transport in Bioelectrochemical Systems towards its Recovery.

We report an integrated experimental and simulation study of ammonia recovery using microbial electrolysis cells (MECs). The transport of various species during the batch-mode operation of an MEC was examined experimentally and the results were used to validate the mathematical model for such an operation. It was found that, while the generated electrical current through the system tends to acidify (or basify) the anolyte (or catholyte), their effects are buffered by a cascade of chemical groups such as the NH3/NH4(+) group, leading to relatively stable pH values in both anolyte and catholyte. The transport of NH4(+) ions accounts for ~90% of the total current, thus quantitatively confirming that the NH4(+) ions serve as effective proton shuttles during MEC operations. Analysis further indicated that, because of the Donnan equilibrium at cation exchange membrane-anolyte/catholyte interfaces, the Na(+) ion in the anolyte actually facilitates the transport of NH4(+) ions during the early stage of a batch cycle and they compete with the NH4(+) ions weakly at later time. These insights, along with a new and simple method for predicting the strength of ammonia diffusion from the catholyte toward the anolyte, will help effective design and operation of bioeletrochemical system-based ammonia recovery systems.

Recovery of nitrogen and water from landfill leachate by a microbial electrolysis cell-forward osmosis system.

A microbial electrolysis cell (MEC)-forward osmosis (FO) system was previously reported for recovering ammonium and water from synthetic solutions, and here it has been advanced with treating landfill leachate. In the MEC, 65.7±9.1% of ammonium could be recovered in the presence of cathode aeration. Without aeration, the MEC could remove 54.1±10.9% of ammonium from the leachate, but little ammonia was recovered. With 2M NH4HCO3 as the draw solution, the FO process achieved 51% water recovery from the MEC anode effluent in 3.5-h operation, higher than that from the raw leachate. The recovered ammonia was used as a draw solute in the FO for successful water recovery from the treated leachate. Despite the challenges with treating returning solution from the FO, this MEC-FO system has demonstrated the potential for resource recovery from wastes, and provide a new solution for sustainable leachate management.

Understanding electricity generation in osmotic microbial fuel cells through integrated experimental investigation and mathematical modeling.

Osmotic microbial fuel cells (OsMFCs) are a new type of MFCs with integrating forward osmosis (FO). However, it is not well understood why electricity generation is improved in OsMFCs compared to regular MFCs. Herein, an approach integrating experimental investigation and mathematical model was adopted to address the question. Both an OsMFC and an MFC achieved similar organic removal efficiency, but the OsMFC generated higher current than the MFC with or without water flux, resulting from the lower resistance of FO membrane. Combining NaCl and glucose as a catholyte demonstrated that the catholyte conductivity affected the electricity generation in the OsMFC. A mathematical model of OsMFCs was developed and validated with the experimental data. The model predicated the variation of internal resistance with increasing water flux, and confirmed the importance of membrane resistance. Increasing water flux with higher catholyte conductivity could decrease the membrane resistance.