Machine Learning for Polymer Design to Enhance Pervaporation-Based Organic Recovery.

Pervaporation (PV) is an effective membrane separation process for organic dehydration, recovery, and upgrading. However, it is crucial to improve membrane materials beyond the current permeability-selectivity trade-off. In this research, we introduce machine learning (ML) models to identify high-potential polymers, greatly improving the efficiency and reducing cost compared to conventional trial-and-error approach. We utilized the largest PV data set to date and incorporated polymer fingerprints and features, including membrane structure, operating conditions, and solute properties. Dimensionality reduction, missing data treatment, seed randomness, and data leakage management were employed to ensure model robustness. The optimized LightGBM models achieved RMSE of 0.447 and 0.360 for separation factor and total flux, respectively (logarithmic scale). Screening approximately 1 million hypothetical polymers with ML models resulted in identifying polymers with a predicted permeation separation index >30 and synthetic accessibility score <3.7 for acetic acid extraction. This study demonstrates the promise of ML to accelerate tailored membrane designs.

Multistage Surface-Heated Vacuum Membrane Distillation Process Enables High Water Recovery and Excellent Heat Utilization: A Modeling Study.

Surface-heated membrane distillation (MD) enhances the energy efficiency of desalination by mitigating temperature polarization (TP). However, systematic investigations of larger scale, multistage, surface-heated MD system with high water recovery and heat recycling are limited. Here, we explore the design and performance of a multistage surface-heated vacuum MD (SHVMD) with heat recovery through a comprehensive finite difference model. In this process, the latent heat of condensation is recovered through an internal heat exchanger (HX) using the retentate from one stage as the condensing fluid for the next stage and an external HX using the feed as the condensing fluid. Model results show that surface heating enhances the performance compared to conventional vacuum MD (VMD). Specifically, in a six-stage SHVMD process, 54.44% water recovery and a gained output ratio (GOR) of 3.28 are achieved with a surface heat density of 2000 W m-2, whereas a similar six-stage VMD process only reaches 18.19% water recovery and a GOR of 2.15. Mass and energy balances suggest that by mitigating TP, surface heating increases the latent heat trapped in vapor. The internal and external HXs capture and reuse the additional heat, which enhances the GOR values. We show for SHVMD that the hybrid internal/external heat recovery design can have GOR value 1.44 times higher than that of systems with only internal or external heat recovery. Furthermore, by only increasing six stages to eight stages, a GOR value as high as 4.35 is achieved. The results further show that surface heating can reduce the energy consumption of MD for brine concentration. The multistage SHVMD technology exhibits a promising potential for the management of brine from industrial plants.

High-Efficiency Recovery of Acetic Acid from Water Using Electroactive Gas-Stripping Membranes.

Recovery of carbon-based resources from waste is a critical need for achieving carbon neutrality and reducing fossil carbon extraction. We demonstrate a new approach for extracting volatile fatty acids (VFAs) using a multifunctional direct heated and pH swing membrane contactor. The membrane is a multilayer laminate composed of a carbon fiber (CF) bound to a hydrophobic membrane and sealed with a layer of polydimethylsiloxane (PDMS); this CF is used as a resistive heater to provide a thermal driving force for PDMS that, while a highly hydrophobic material, is known for its ability to rapidly pass gases, including water vapor. The transport mechanism for gas transport involves the diffusion of molecules through the free volume of the polymer matrix. CF coated with polyaniline (PANI) is used as an anode to induce an acidic pH swing at the interface between the membrane and water, which can protonate the VFA molecule. The innovative multilayer membrane used in this study has successfully demonstrated a highly efficient recovery of VFAs by simultaneously combining pH swing and joule heating. This novel technique has revealed a new concept in the field of VFA recovery, offering promising prospects for further advancements in this area. The energy consumption was 3.37 kWh/kg for acetic acid (AA), and an excellent separation factor of AA/water of 51.55 ± 2.11 was obtained with high AA fluxes of 51.00 ± 0.82 g.m-2hr-1. The interfacial electrochemical reactions enable the extraction of VFAs without the need for bulk temperature and pH modification.

Simple and Low-Cost Electroactive Membranes for Ammonia Recovery.

Ammonia is considered a contaminant to be removed from wastewater. However, ammonia is a valuable commodity chemical used as the primary feedstock for fertilizer manufacturing. Here we describe a simple and low-cost ammonia gas stripping membrane capable of recovering ammonia from wastewater. The material is composed of an electrically conducting porous carbon cloth coupled to a porous hydrophobic polypropylene support, that together form an electrically conductive membrane (ECM). When a cathodic potential is applied to the ECM surface, hydroxide ions are produced at the water-ECM interface, which transforms ammonium ions into higher-volatility ammonia that is stripped across the hydrophobic membrane material using an acid-stripping solution. The simple structure, low cost, and easy fabrication process make the ECM an attractive material for ammonia recovery from dilute aqueous streams, such as wastewater. When paired with an anode and immersed into a reactor containing synthetic wastewater (with an acid-stripping solution providing the driving force for ammonia transport), the ECM achieved an ammonia flux of 141.3 ± 14.0 g.cm-2.day-1 at a current density of 6.25 mA.cm-2 (69.2 ± 5.3 kg(NH3-N)/kWh). It was found that the ammonia flux was sensitive to the current density and acid circulation rate.

Nitrate Removal in an Electrically Charged Granular-Activated Carbon Column.

Nitrate removal from groundwater remains a challenge. Here, we report on the development of a flow-through, electrically charged, granular-activated carbon (GAC)-filled column, which effectively removes nitrate. In this system, the GAC functioned as an anode, while a titanium sheet acted as a cathode. The high removal rate of nitrate was achieved through a combination of electrosorption and electrochemical transformation to N2. The column could be readily regenerated in situ by reversing the polarity of the applied potential. We demonstrate that in the presence of chloride, the mechanism responsible for the observed nitrate removal involves a combination of electroadsorption of nitrate to the anodically charged GAC, electroreduction of nitrate to ammonium, and the oxidation of ammonium to N2 gas by reactive chlorine and other oxidative radicals (with nearly 100% N2 selectivity). Given the ubiquitous presence of chloride in groundwater, this method represents a ready, green, and sustainable treatment process with significant potential for the remediation of contaminated groundwater.

Linker-Free Magnetite-Decorated Gold Nanoparticles (Fe3O4-Au): Synthesis, Characterization, and Application for Electrochemical Detection of Arsenic (III).

Linker-free magnetite nanoparticles (Fe3O4NPs)-decorated gold nanoparticles (AuNPs) were grown using a new protocol that can be used as a new platform for synthesis of other intact metal-metal oxide nanocomposites without the need for linkers. This minimizes the distance between the metal and metal oxide nanoparticles and ensures the optimum combined effects between the two material interfaces. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy confirmed the successful synthesis of the Fe3O4-Au nanocomposite, without any change in the magnetite phase. Characterization, using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, revealed the composite to consist of AuNPs of 70 ± 10 nm diameter decorated with tiny 10 ± 3 nm diameter Fe3O4NPs in Au:Fe mass ratio of 5:1. The prepared Fe3O4-Au nanocomposite was embedded in ionic liquid (IL) and applied for the modification of glassy carbon electrode (GCE) for the electrochemical detection of As(III) in water. By combining the excellent catalytic properties of the AuNPs with the high adsorption capacity of the tiny Fe3O4NPs towards As(III), as well as the good conductivity of IL, the Fe3O4-Au-IL nanocomposite showed excellent performance in the square wave anodic stripping voltammetry detection of As(III). Under the optimized conditions, a linear range of 1 to 100 µg/L was achieved with a detection limit of 0.22 µg/L (S/N = 3), and no interference from 100-fold higher concentrations of a wide variety of cations and anions found in water. A very low residual standard deviation of 1.16% confirmed the high precision/reproducibility of As(III) analysis and the reliability of the Fe3O4-Au-IL sensing interface. Finally, this proposed sensing interface was successfully applied to analyzing synthetic river and wastewater samples with a 95-101% recovery, demonstrating excellent accuracy, even in complex synthetic river and wastewater samples containing high concentrations of humic acid without any sample pretreatments.

Electroactive Membranes for Water Treatment: Enhanced Treatment Functionalities, Energy Considerations, and Future Challenges.

To meet the increasing demand for water, potable water providers are turning toward unconventional waters, such as seawater and wastewater. These highly saline and/or heavily contaminated water sources are difficult to treat, demanding the use of advanced technology not typically used to treat conventional water sources such as river water or fresh groundwater. Of these advanced technologies, membrane separation processes are fast becoming the most widely used methods to convert these marginal waters into useful resources. The main factors contributing to the widespread adoption of membrane separation processes for water treatment include their modular nature, small physical footprint, and relative energy efficiency compared to traditional distillation processes. In addition, membranes present a physical barrier to pathogens, which is an attractive feature in terms of disinfection credits. However, traditional membrane materials suffer from several distinct drawbacks, which include membrane fouling (the accumulation of material on the membrane surface that blocks the flow of water), the need for high-pressure membranes (such as reverse osmosis (RO) or nanofiltration (NF)) or membrane/thermal processes (e.g., membrane distillation (MD)) to remove small contaminant compounds (e.g., trace metals, salt, endocrine disrupting compounds), and a pressure-driven membrane's inability to effectively remove small, uncharged molecules (e.g., N-nitrosodimethylamine (NDMA), phenol, acetone, and boron). Electrically driven physical and chemical phenomena, such as electrophoresis, electrostatic repulsion, dielectrophoresis, and electricity-driven redox reactions, have long been coupled to membrane-based separation processes, in a process known as electrofiltration. However, it is only in recent years that appropriate membrane materials (i.e., electrically conducting membranes (EMs)) have been developed that enable the efficient use of these electro-driven processes. Specifically, the development of EM materials (both polymeric and inorganic) have reduced the energy consumption of electrofiltration by using the membrane as an electrode in an electrochemical circuit. In essence, a membrane-electrode allows for the concentrated delivery of electrical energy directly to the membrane/water interface where the actual separation process takes place. In the past, metal electrodes were placed on either side of the membrane, which resulted in large potentials needed to drive electrochemical/electrokinetic phenomena. The use of a membrane-electrode dramatically reduces the required potentials, which reduces energy consumption and can also eliminate electrocorrosion and the formation of undesirable byproducts. In this Account, we review recent developments in the field of electrofiltration, with a focus on two water treatment applications: desalination and water reuse (wastewater or contaminated groundwater recycling). Specifically, we discuss how EMs can be used to minimize multiple forms of fouling (biofouling, mineral scaling, organic fouling); how electrochemical reactions at the membrane/water interface are used to destroy toxic contaminants, clean a membrane surface, and transform the local pH environment, which enhances the rejection of certain contaminants; how electric fields and electrostatic forces can be used to reorient molecules at the membrane/water interface; and how electrical energy can be transformed into thermal energy to drive separation processes. A special emphasis is placed on explicitly defining the additional energy consumption associated with the electrochemical phenomena, as well as the additional cost associated with fabricating EM materials. In addition, we will discuss current limitations of the electrofiltration process, with particular attention given to the current limitations of membrane materials and the future research needs in the area of membrane materials and module development.

Structural Dependence of Reductive Defluorination of Linear PFAS Compounds in a UV/Electrochemical System.

Per and polyfluoroalkyl substances (PFAS), legacy chemicals used in firefighting and the manufacturing of many industrial and consumer goods, are widely found in groundwater resources, along with other regulated compounds, such as chlorinated solvents. Due to their strong C-F bonds, these molecules are extremely recalcitrant, requiring advanced treatment methods for effective remediation, with hydrated electrons shown to be able to defluorinated these compounds. A combined photo/electrochemical method has been demonstrated to dramatically increase defluorination rates, where PFAS molecules sorbed onto appropriately functionalized cathodes charged to low cell potentials (-0.58 V vs Ag/AgCl) undergo a transient electron transfer event from the electrode, which "primes" the molecule by reducing the C-F bond strength and enables the bond's dissociation upon the absorption of a hydrated electron. In this work, we explore the impact of headgroup and chain length on the performance of this two-electron process and extend this technique to chlorinated solvents. We use isotopically labeled PFAS molecules to take advantage of the kinetic isotope effect and demonstrate that indeed PFAS defluorination is likely driven by a two-electron process. We also present density functional theory calculations to illustrate that the externally applied potential resulted in an increased rate of electron transfer, which ultimately increased the measured defluorination rate.

Mineral Scale Prevention on Electrically Conducting Membrane Distillation Membranes Using Induced Electrophoretic Mixing.

The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.

The interactions and adsorption mechanisms of ternary heavy metals on boron nitride.

In this work, the interactions and adsorption mechanisms of Cu2+, Cd2+, and Ni2+ on boron nitride (BN) were tested by the simultaneous removal of metal ions from synthetic wastewater. BN was characterized using XRD, SEM, and FTIR spectroscopy. The adsorption differences between BN and the metal ions were explored through comparative studies in a single and ternary system. In the ternary system, adsorption occurs rapidly in the first 2 min for the metal ions, and the affinity order follows Cu2+>Cd2+>Ni2+. However, adsorption behavior changes due to the interaction between metal ions in the ternary system. Cu2+ showed an antagonistic effect on the adsorption of Cd2+ and Ni2+, while Cd2+ and Ni2+ produced a synergistic effect on Cu2+. In addition, the effect of metal ion concentration on the interaction between ions was studied based on a surface response experiment. An increase in Ni2+ or Cd2+ concentrations plays a synergistic effect on the adsorption of Cu2+, while an antagonistic adsorption for Ni2+ occurred with increasing Cu2+ or Cd2+ concentrations. We also discussed the various adsorption mechanisms as complexation, ion exchange, and electrostatic adsorption based on XPS analysis.

Bismuth Subcarbonate Decorated Reduced Graphene Oxide Nanocomposite for the Sensitive Stripping Voltammetry Analysis of Pb(II) and Cd(II) in Water.

In this paper, bismuth subcarbonate (BiO)2CO3-reduced graphene oxide nanocomposite incorporated in Nafion matrix ((BiO)2CO3-rGO-Nafion) was synthesized and further applied, for the first time, in the sensitive detection of Pb(II) and Cd(II) by square-wave anodic stripping voltammetry (SWASV). The as-synthesized nanocomposites were characterized by energy-dispersive spectroscopy (EDS), Raman spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). (BiO)2CO3 composite plays a key role in the improvement of the detection sensitivity, which can form multicomponent alloy with cadmium and lead. Additionally, the unique structure of rGO can enlarge the surface area and provide abundant active sites. Moreover, Nafion incorporation in the nanocomposite can effectively increase the adhesion and mechanical strength of the film, and further improve the preconcetration ability due to the cation-exchange capacity of its abundant sulfonate groups. As expected, the (BiO)2CO3-rGO/Nafion nanocomposite-modified glassy carbon electrode ((BiO)2CO3-rGO-Nafion/GCE) achieved low detection limits of 0.24 µg/L for Pb(II) and 0.16 µg/L for Cd(II), in the linear range of 1.0-60 µg/L, and showed some excellent performance, such as high stability, good selectivity, and sensitivity. Finally, synthetic water samples were prepared and further used to verify the practicability of the (BiO)2CO3-rGO-Nafion/GCE with satisfactory results.

Hydrophobic Gas Transfer Membranes for Wastewater Treatment and Resource Recovery.

Gaseous compounds, such as CH4, H2, and O2, are commonly produced or consumed during wastewater treatment. Traditionally, these gases need to be removed or delivered using gas sparging or liquid heating, which can be energy intensive with low efficiency. Hydrophobic membranes are being increasingly investigated in wastewater treatment and resource recovery. This is because these semipermeable barriers repel water and create a three-phase interface that enhances mass transfer and chemical conversions. This Critical Review provides a first comprehensive analysis of different hydrophobic membranes and processes, and identifies the challenges and potential for future system development. The discussions and analyses were grouped based on mechanisms and applications, including membrane gas extraction, membrane gas delivery, and hybrid processes. Major challenges, such as membrane fouling, wetting, and limited selectivity and functionality, are identified, and potential solutions articulated. New opportunities, such as electrochemical coating, integrated membrane electrodes, and membrane functionalization, are also discussed to provide insights for further development of more efficient and low-cost membranes and processes.

Stable Superhydrophobic Ceramic-Based Carbon Nanotube Composite Desalination Membranes.

Membrane distillation (MD) is a promising process for the treatment of highly saline wastewaters. The central component of MD is a stable porous hydrophobic membrane with a large liquid-vapor interface for efficient water vapor transport. A key challenge for current polymeric or hydrophobically modified inorganic membranes is insufficient operating stability, resulting in some issues such as wetting, fouling, flux, and rejection decline. This study presents an overall conceptual design and application strategy for a superhydrophobic ceramic-based carbon nanotube (CNT) desalination membrane having specially designed membrane structures with unprecedented operating stability and MD performance. Superporous and superhydrophobic surface structures with CNT networks are created after quantitative regulation of in situ grown CNT. The fully covered CNT layers (FC-CNT) exhibit significantly improved thermally and superhydrophobically stable properties under an accelerated stability test. Due to the distinctive structure of the superporous surface network, providing a large liquid-vapor superhydrophobic interface and interior finger-like macrovoids, the FC-CNT membrane exhibits a stable high flux with a 99.9% rejection of Na+, outperforming existing inorganic membranes. Under simple and nondestructive electrochemically assisted direct contact MD (e-DCMD), enhanced antifouling performance is observed. The design strategy is broadly applicable to be extended toward fabrication of high performance membranes derived from other ceramic or inorganic substrates and additional applications in wastewater and gas treatment.

Field-Induced Redistribution of Surfactants at the Oil/Water Interface Reduces Membrane Fouling on Electrically Conducting Carbon Nanotube UF Membranes.

Membrane-based treatment of oily wastewater remains a significant challenge, particularly under high salinity conditions. The main difficulty associated with this separation process is membrane fouling, mostly caused by wetting and coalescence of emulsified oil droplets on the membrane surface. In this study, electrically conducting carbon nanotube-based ultrafiltration membranes were used to treat an emulsified oil suspension at ionic strengths as high as 100 mM. By tuning the electrical potential applied to the membrane surface, we demonstrate how fouling can be dramatically reduced, even under high salinity conditions. Permeate water quality is shown to improve upon application of a negative potential. Using optical microscopy, we observed dramatic changes in the shape of oil droplets at the membrane/water interface in response to the applied electric potential; this change is associated with a redistribution of charged surfactant molecules at the oil/water interface in response to the external electric field. Specifically, using the membrane as a cathode repels surfactant molecules away from the oil/membrane interface, while anodic conditions lead to increased surfactant concentrations. We speculate that this change in surfactant molecule distribution is responsible for changes in the surface tension of oil droplets at the membrane/water interface, which results in a decrease in oil coalescence and subsequent fouling. The membranes used in this study offer an attractive treatment option when separating emulsified oil from water under high salinity conditions.

Nickel-Based Membrane Electrodes Enable High-Rate Electrochemical Ammonia Recovery.

Wastewater contains significant amounts of nitrogen that can be recovered and valorized as fertilizers and chemicals. This study presents a new membrane electrode coupled with microbial electrolysis that demonstrates very efficient ammonia recovery from synthetic centrate. The process utilizes the electrical potential across electrodes to drive NH4+ ions toward the hydrophilic nickel top layer on a gas-stripping membrane cathode, which takes advantage of surface pH increase to realize spontaneous NH3 production and separation. Compared with a control configuration with conventionally separated electrode and hydrophobic membrane, the integrated membrane electrode showed 40% higher NH3-N recovery rate (36.2 ± 1.2 gNH3-N/m2/d) and 11% higher current density. The energy consumption was 1.61 ± 0.03 kWh/kgNH3-N, which was 20% lower than the control and 70-90% more efficient than competing electrochemical nitrogen recovery processes (5-12 kWh/kgNH3-N). Besides, the negative potential on membrane electrode repelled negatively charged organics and microbes thus reduced fouling. In addition to describing the system's performance, we explored the underlying mechanisms governing the reactions, which confirmed the viability of this process for efficient wastewater-ammonia recovery. Furthermore, the nickel-based membrane electrode showed excellent water entry pressure (∼41 kPa) without leakage, which was much higher than that of PTFE/PDMS-based cathodes (∼1.8 kPa). The membrane electrode also showed superb flexibility (180° bend) and can be easily fabricated at low cost (<20 $/m2).

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H2O2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Wastewater Reuse for Agriculture: Development of a Regional Water Reuse Decision-Support Model (RWRM) for Cost-Effective Irrigation Sources.

Water scarcity has become a critical problem in many semiarid and arid regions. The single largest water use in such regions is for crop irrigation, which typically relies on groundwater and surface water sources. With increasing stress on these traditional water sources, it is important to consider alternative irrigation sources for areas with limited freshwater resources. One potential irrigation water resource is treated wastewater for agricultural fields located near urban centers. In addition, treated wastewater can contribute an appreciable amount of necessary nutrients for plants. The suitability of reclaimed water for specific applications depends on water quality and usage requirements. The main factors that determine the suitability of recycled water for agricultural irrigation are salinity, heavy metals, and pathogens, which cause adverse effects on human, plants, and soils. In this paper, we develop a regional water reuse decision-support model (RWRM) using the general algebraic modeling system to analyze the cost-effectiveness of alternative treatment trains to generate irrigation water from reclaimed wastewater, with the irrigation water designed to meet crop requirements as well as California's wastewater reuse regulations (Title 22). Using a cost-minimization framework, least-cost solutions consisting of treatment processes and their intensities (blending ratios) are identified to produce alternative irrigation sources for citrus and turfgrass. Our analysis illustrates the benefits of employing an optimization framework and flexible treatment design to identify cost-effective blending opportunities that may produce high-quality irrigation water for a wide range of end uses.

Microbial Attachment Inhibition through Low-Voltage Electrochemical Reactions on Electrically Conducting Membranes.

Bacterial biofilm formation on membrane surfaces remains a serious challenge in water treatment systems. The impact of low voltages on microbial attachment to electrically conducting ultrafiltration membranes was investigated using a direct observation cross-flow membrane system mounted on a fluorescence microscope. Escherichia coli and microparticle deposition and detachment rates were measured as a function of the applied electrical potential to the membrane surface. Selecting bacteria and particles with low surface charge minimized electrostatic interactions between the bacteria and charged membrane surface. Application of an electrical potential had a significant impact on the detachment of live bacteria in comparison to dead bacteria and particles. Image analysis indicated that when a potential of 1.5 V was applied to the membrane/counter electrode pair, the percent of dead bacteria was 32±2.1 and 67±3.6% when the membrane was used as a cathode or anode, respectively, while at a potential of 1 V, 92±2.4% were alive. The application of low electrical potentials resulted in the production of low (µM) concentrations of hydrogen peroxide (HP) through the electroreduction of oxygen. The electrochemically produced HP reduced microbial cell viability and increased cellular permeability. Exposure to low concentrations of electrochemically produced HP on the membrane surface prevents bacterial attachment, thus ensuring biofilm-free conditions during membrane filtration operations.

Aquatic biofouling prevention by electrically charged nanocomposite polymer thin film membranes.

Electrically conductive polymer-nanocomposite (ECPNC) tight nanofiltration (NF) thin film membranes were demonstrated to have biofilm-preventing capabilities under extreme bacteria and organic material loadings. A simple route to the creation and application of these polyamide-carbon nanotube thin films is also reported. These thin films were characterized with SEM and TEM as well as FTIR to demonstrate that the carbon nanotubes are embedded within the polyamide and form ester bonds with trimesoyl chloride, one of the monomers of polyamide. These polymer nanocomposite thin film materials boast high electrical conductivity (∼400 S/m), good NaCl rejection (>95%), and high water permeability. To demonstrate these membranes' biofouling capabilities, we designed a cross-flow water filtration vessel with insulated electrical leads connecting the ECPNC membranes to an arbitrary waveform generator. In all experiments, conducted in highly bacterially contaminated LB media, flux tests were run until fluxes decreased by 45 ± 3% over initial flux. Biofilm-induced, nonreversible flux decline was observed in all control experiments and a cross-flow rinse with the feed solution failed to induce flux recovery. In contrast, flux decrease for the ECPNC membranes with an electric potential applied to their surface was only caused by deposition of bacteria rather than bacterial attachment, and flux was fully recoverable following a short rinse with the feed solution and no added cleaning agents. The prevention of biofilm formation on the ECPNC membranes was a long-term effect, did not decrease with use, and was highly reproducible.

Electrolytic Seawater Mineralization and the Mass Balances That Demonstrate Carbon Dioxide Removal.

We present the mass balances associated with carbon dioxide (CO2) removal (CDR) using seawater as both the source of reactants and as the reaction medium via electrolysis following the "Equatic" (formerly known as "SeaChange") process. This process, extensively detailed in La Plante E.C.; ACS Sustain. Chem. Eng.2021, 9, ( (3), ), 1073-1089, involves the application of an electric overpotential that splits water to form H+ and OH- ions, producing acidity and alkalinity, i.e., in addition to gaseous coproducts, at the anode and cathode, respectively. The alkalinity that results, i.e., via the "continuous electrolytic pH pump" results in the instantaneous precipitation of calcium carbonate (CaCO3), hydrated magnesium carbonates (e.g., nesquehonite: MgCO3·3H2O, hydromagnesite: Mg5(CO3)4(OH)2·4H2O, etc.), and/or magnesium hydroxide (Mg(OH)2) depending on the CO32- ion-activity in solution. This results in the trapping and, hence, durable and permanent (at least ∼10 000-100 000 years) immobilization of CO2 that was originally dissolved in water, and that is additionally drawn down from the atmosphere within: (a) mineral carbonates, and/or (b) as solvated bicarbonate (HCO3-) and carbonate (CO32-) ions (i.e., due to the absorption of atmospheric CO2 into seawater having enhanced alkalinity). Taken together, these actions result in the net removal of ∼4.6 kg of CO2 per m3 of seawater catholyte processed. Geochemical simulations quantify the extents of net CO2 removal including the dependencies on the process configuration. It is furthermore indicated that the efficiency of realkalinization of the acidic anolyte using alkaline solids depends on their acid neutralization capacity and dissolution reactivity. We also assess changes in seawater chemistry resulting from Mg(OH)2 dissolution with emphasis on the change in seawater alkalinity and saturation state. Overall, this analysis provides direct quantifications of the ability of the Equatic process to serve as a means for technological CDR to mitigate the worst effects of accelerating climate change.