Unlocking the Potential of Nanobubbles: Achieving Exceptional Gas Efficiency in Electrogeneration of Hydrogen Peroxide.

The electrogeneration of hydrogen peroxide (H2 O2 ) via the oxygen reduction reaction is a crucial process for advanced water treatment technologies. While significant effort is being devoted to developing highly reactive materials, gas provision systems used in these processes are receiving less attention. Here, using oxygen nanobubbles to improve the gas efficiency of the electrogeneration of H2 O2 is proposed. Aeration with nanobubbles is compared to aeration with macrobubbles under an identical experimental set-up, with nanobubbles showing a much higher gas-liquid volumetric mass transfer coefficient (KL a) of 2.6 × 10-2 min-1 compared to 2.7 × 10-4 min-1 for macrobubbles. Consequently, nanobubbles exhibit a much higher gas efficiency using 60% of O2 delivered to the system compared to 0.19% for macrobubbles. Further, it is observed that the electrogeneration of H2 O2 using carbon felt electrodes is enhanced using nanobubbles. Under the same dissolved oxygen levels, nanobubbles boost the reaction yield to 84%, while macrobubbles yield only 53.8%. To the authors' knowledge, this is the first study to investigate the use of nanobubbles in electrochemical reactions and demonstrate their ability to enhance gas efficiency and electrocatalytic response. These findings have important implications for developing more efficient chemical and electrochemical processes operating under gas-starving systems.

Amino-modified upcycled biochar achieves selective chromium removal in complex aqueous matrices.

Chromium pollution of groundwater sources is a growing global issue, which correlates with various anthropogenic activities. Remediation of both the Cr(VI) and Cr(III), via adsorption technologies, has been championed in recent years due to ease of use, minimal energy requirements, and the potential to serve as a highly sustainable remediation technology. In the present study, a biochar sorbent sourced from pineapple skins, allowed for the upcycling of agricultural waste into water purification technology. The biochar material was chemically modified, through a green amination method, to produce an efficient and selective adsorbent for the removal of both Cr(VI) and Cr(III) from complex aqueous matrices. From FTIR analysis it was evident that the chemical modification introduced new C-N and N-H bonds observed in the modified biochar along with a depletion of N-O and C-H bonds found in the pristine biochar. The amino modified biochar was found to spontaneously adsorb both forms of chromium at room temperature, with binding capacities of 46.5 mg/g of Cr(VI) and 27.1 mg/g of Cr(III). Interference studies, conducted in complex matrices, showed no change in adsorption capacity for Cr(VI) in matrices containing up to 3,000× the concentration of interfering ions. Finally, Cr(III) removal was synergized to 100% adsorption at interfering ions concentrations up to 330× of the analyte, which were suppressed at higher interference concentrations. Considering such performance, the amino modified biochar achieved selective removal for both forms of chromium, showing great potential for utilization in complex chromium pollution sources.

Enhancing the selective ciprofloxacin adsorption in urine matrices through the metal-doping of carbon sorbents.

Pharmaceuticals excreted after administration can pollute water sources given their ineffective removal in conventional wastewater treatment plant. Among the techniques used during tertiary wastewater treatment, adsorption is an effective and cost-efficient method for removing antibiotics. This study aimed to investigate the adsorption of ciprofloxacin (CIP) on metal-doped granular activated carbon (GAC) and evaluate the impact of urine on CIP adsorption for pristine, pre-oxidized, and metal-doped GAC. The results showed that the uptake of CIP by iron (Fe)-doped GAC was higher than Ag-doped, pre-oxidized, and pristine GAC in single-solute isotherms (DI water). This higher uptake was attributed to the presence of Fe content (1.2%) on the carbon surface, which can strongly interact with zwitterionic CIP at a neutral pH. However, when synthetic human urine was introduced, the adsorption of CIP was negatively affected due to pore blockage and competition for available sorption sites on the GAC. Among the four types of GACs tested, the lowest reduction in CIP uptake in the urine solution was observed for Fe-doped GAC followed (%17) by pre-oxidized (64%), Ag-doped (%69), and pristine F400 (76%) carbon. These results suggested that the complexation between CIP and Fe-doped GAC in urine was stronger due to its higher functionalization compared to Ag-doped, pre-oxidized, and pristine GAC. As the equilibrium concentration of CIP increased, the competition between CIP and urine decreased on the surface of Fe-doped carbon, owing to the limited competition from urine for the available active sorption sites.

Unified Metallic Catalyst Aging Strategy and Implications for Water Treatment.

Heterogeneous catalysis holds great promise for oxidizing or reducing a range of pollutants in water. A well-recognized, but understudied, barrier to implement catalytic treatment centers around fouling or aging over time of the catalyst surfaces. To better understand how to study catalyst fouling or aging, we selected a representative bimetallic catalyst (Pd-In supported on Al2O3), which holds promise to reduce nitrate to innocuous nitrogen gas byproducts upon hydrogen addition, and six model solutions (deionized water, sodium hypochlorite, sodium borohydride, acetic acid, sodium sulfide, and tap water). Our novel aging experimental apparatus permitted single passage of each model solution, separately, through a small packed-bed reactor containing replicate bimetallic catalyst "beds" that could be sacrificed weekly for off-line characterization to quantify impacts of fouling or aging. The composition of the model solutions led to the following gradual changes in surface composition, morphology, or catalytic reactivity: (i) formation of passivating species, (ii) decreased catalytic sites due to metal leaching under acid conditions or sulfide poisoning, (iii) dissolution and/or transformation of indium, (iv) formation of new catalytic sites by the introduction of an additional metallic element, and (v) oxidative etching. The model solution water chemistry captured a wide range of conditions likely to be encountered in potable or industrial water treatment. Aging-induced changes altered catalytic activity and provided insights into potential strategies to improve long-term catalyst operations for water treatment.

Silver Enhances Hematite Nanoparticles Based Ethanol Sensor Response and Selectivity at Room Temperature.

Gas sensors are fundamental for continuous online monitoring of volatile organic compounds. Gas sensors based on semiconductor materials have demonstrated to be highly competitive, but are generally made of expensive materials and operate at high temperatures, which are drawbacks of these technologies. Herein is described a novel ethanol sensor for room temperature (25 °C) measurements based on hematite (α­Fe2O3)/silver nanoparticles. The AgNPs were shown to increase the oxide semiconductor charge carrier density, but especially to enhance the ethanol adsorption rate boosting the selectivity and sensitivity, thus allowing quantification of ethanol vapor in 2-35 mg L-1 range with an excellent linear relationship. In addition, the α-Fe2O3/Ag 3.0 wt% nanocomposite is cheap, and easy to make and process, imparting high perspectives for real applications in breath analyzers and/or sensors in food and beverage industries. This work contributes to the advance of gas sensing at ambient temperature as a competitive alternative for quantification of conventional volatile organic compounds.

Dimensionally Stable Anode Based Sensor for Urea Determination via Linear Sweep Voltammetry.

Urea is an added value chemical with wide applications in the industry and agriculture. The release of urea waste to the environment affects ecosystem health despite its low toxicity. Online monitoring of urea for industrial applications and environmental health is an unaddressed challenge. Electroanalytical techniques can be a smart integrated solution for online monitoring if sensors can overcome the major barrier associated with long-term stability. Mixed metal oxides have shown excellent stability in environmental conditions with long lasting operational lives. However, these materials have been barely explored for sensing applications. This work presents a proof of concept that demonstrates the applicability of an indirect electroanalytical quantification method of urea. The use of Ti/RuO2-TiO2-SnO2 dimensional stable anode (DSA®) can provide accurate and sensitive quantification of urea in aqueous samples exploiting the excellent catalytic properties of DSA® on the electrogeneration of active chlorine species. The cathodic reduction of accumulated HClO/ClO- from anodic electrogeneration presented a direct relationship with urea concentration. This novel method can allow urea quantification with a competitive LOD of 1.83 × 10-6 mol L-1 within a linear range of 6.66 × 10-6 to 3.33 × 10-4 mol L-1 of urea concentration.

Bismuth Film-Coated Gold Ultramicroelectrode Array for Simultaneous Quantification of Pb(II) and Cd(II) by Square Wave Anodic Stripping Voltammetry.

The widespread presence of heavy metals in drinking water sources arises as a major health concern, particularly in developing countries. The development of low-cost and reliable detection techniques is identified as a societal need to provide affordable water quality control. Herein, a bismuth film-coated gold ultramicroelectrode array (BF-UMEA) was used for the detection of Pb(II) and Cd(II) in water samples via square wave anodic stripping voltammetry (SWASV). Experimental parameters such as deposition time, Bi(III) concentration, acetate buffer concentration, pH, square wave frequency, amplitude, and step potential were all varied to determine their effects on the current peak intensities of the target metal ions. Ten-fold excess in the concentration of interferences was found to cause a decrease in the stripping peak areas of Cd(II) and Pb(II) in the following order of magnitude: benzene < NaCl < Ni(II) < Cu(II). Using Box-Behnken design, the optimum SWASV parameters that provided maximum current peak areas were 14.76 Hz (frequency), 50.10 mV (amplitude), and 8.76 mV (step potential). The limits of detection of the as-prepared BF-UMEA were 5 and 7 µg L-1 for Pb(II) and Cd(II), respectively. These results demonstrate the potential use of a BF-UMEA in SWASV for the trace quantification of Pb(II) and Cd(II) in water samples.

The Surge of Metal-Organic-Framework (MOFs)-Based Electrodes as Key Elements in Electrochemically Driven Processes for the Environment.

Metal-organic-frameworks (MOFs) are emerging materials used in the environmental electrochemistry community for Faradaic and non-Faradaic water remediation technologies. It has been concluded that MOF-based materials show improvement in performance compared to traditional (non-)faradaic materials. In particular, this review outlines MOF synthesis and their application in the fields of electron- and photoelectron-Fenton degradation reactions, photoelectrocatalytic degradations, and capacitive deionization physical separations. This work overviews the main electrode materials used for the different environmental remediation processes, discusses the main performance enhancements achieved via the utilization of MOFs compared to traditional materials, and provides perspective and insights for the further development of the utilization of MOF-derived materials in electrified water treatment.

Catalytic Converters for Water Treatment.

Fresh water demand is driven by human consumption, agricultural irrigation, and industrial usage and continues to increase along with the global population. Improved methods to inexpensively and sustainably clean water unfit for human consumption are desired, particularly at remote or rural locations. Heterogeneous catalysts offer the opportunity to directly convert toxic molecules in water to nontoxic products. Heterogeneous catalytic reaction processes may bring to mind large-scale industrial production of chemicals, but they can also be used at the small scale, like catalytic converters used in cars to break down gaseous pollutants from fuel combustion. Catalytic processes may be a competitive alternative to conventional water treatment technologies. They have much faster kinetics and are less operationally sensitive than current bioremediation-based methods. Unlike other conventional water treatment technologies (i.e., ion exchange, reverse osmosis, activated carbon filtration), they do not transfer contaminants into separate, more concentrated waste streams. In this Account, we review our efforts on the development of heterogeneous catalysts as advanced reduction technologies to treat toxic water contaminants such as chlorinated organics and nitrates. Fundamental understanding of the underlying chemistry of catalytic materials can inform the design of superior catalytic materials. We discuss the impact of the catalytic structure (i.e., the arrangement of metal atoms on the catalyst surface) on the catalyst activity and selectivity for these aqueous reactions. To explore these aspects, we used model metal-on-metal nanoparticle catalysts along with state-of-the-art in situ spectroscopic techniques and density functional theory calculations to deduce the catalyst surface structure and how it affects the reaction pathways and hence the activity and selectivity. We also discuss recent developments in photocatalysis and electrocatalysis for the treatment of nitrates, touching on fundamentals and surface reaction mechanisms. Finally, we note that despite over 20 years of growing research into heterogeneous catalytic systems for water contaminants, only a few pilot-scale studies have been conducted, with no large-scale implementation to date. We conceive of modular, on- or off-grid catalytic units that treat drinking water at the household tap, at a community well, or for larger-scale reuse of agricultural runoff. We discuss how these may be enhanced by combination with photocatalytic or electrocatalytic processes and how these reductive catalytic modules (catalytic converters for water) can be coupled with other modules for the removal of potential water contaminants.

Nanobubble Technologies Offer Opportunities To Improve Water Treatment.

Since first hypothesizing the existence of nanobubbles (NBs) in 1994, the empirical study of NB properties and commercialization of NB generators have rapidly evolved. NBs are stable spherical packages of gas within liquid and are operationally defined as having diameters less than 1000 nm, though they are typically in the range of 100 nm in one dimension. While theories still lack the ability to explain empirical evidence for formation of stable NBs in water, numerous NB applications have emerged in different fields, including water and wastewater purification where NBs offer the potential to replace or improve efficiency of current treatment processes. The United Nations identifies access to safe drinking water as a human right, and municipal and industrial wastewaters require purification before they enter water bodies. These protections require treatment technologies to remove naturally occurring (e.g., arsenic, chromium, fluoride, manganese, radionuclides, salts, selenium, natural organic matter, algal toxins), or anthropogenic (e.g., nitrate, phosphate, solvents, fuel additives, pharmaceuticals) chemicals and particles (e.g., virus, bacteria, oocysts, clays) that cause toxicity or aesthetic problems to make rivers, lakes, seawater, groundwater, or wastewater suitable for beneficial use or reuse in complex and evolving urban and rural water systems. NBs raise opportunities to improve current or enable new technologies for producing fewer byproducts and achieving safer water. This account explores the potential to exploit the unique properties of NBs for improving water treatment by answering key questions and proposing research opportunities regarding (1) observational versus theoretical existence of NBs, (2) ability of NBs to improve gas transfer into water or influence gas trapped on particle surfaces, (3) ability to produce quasi-stable reactive oxygen species (ROS) on the surface of NBs to oxidize pollutants and pathogens in water, (4) ability to improve particle aggregation through intraparticle NB bridging, and (5) ability to mitigate fouling on surfaces. We conclude with key insights and knowledge gaps requiring research to advance the use of NBs for water purification. Among the highest priorities is to develop techniques that measure NB size and surface properties in complex drinking and wastewater chemistries, which contain salts, organics, and a wide variety of inorganic and organic colloids. In the authors' opinion, ROS production by NB may hold the greatest promise for usage in water treatment because it allows movement away from chemical-based oxidants (chlorine, ozone) that are costly, dangerous to handle, and produce harmful byproducts while helping achieve important treatment goals (e.g., destruction of organic pollutants, pathogens, biofilms). Because of the low chemical requirements to form NBs, NB technologies could be distributed throughout rapidly changing and increasingly decentralized water treatment systems in both developed and developing countries.

Nanoparticle and Transparent Polymer Coatings Enable UV-C Side-Emission Optical Fibers for Inactivation of Escherichia coli in Water.

Pathogenic bacteria pose a health threat and operational challenge in drinking water. UV-C light-emitting diodes (UV-C LEDs) are becoming a competitive disinfection technology but are limited by their small irradiation area. Side-emitting optical fibers (SEOFs) can serve as a UV-C LED light delivery technology for reactors or tubing. Modifying the surfaces of conventional optical fibers with scattering centers allows for side emission of 265 nm radiation from an LED for microbial inactivation in water. Solid-material absorbance and flux measurements differentiated light absorption from scattering for all materials. Silica spheres >200 nm in diameter achieved higher scattering than smaller silica. A critical discovery was that treating the silica-coated optical fiber in a solution of high ionic strength increased UV-C side emission by greater than 6-fold. Additionally, the cladding polymer Cytop had negligible absorbance at 265 nm wavelength. A scalable four-step treatment process was developed to fabricate the novel SEOF. Attached to a 265 nm LED, the side-emitting optical fiber achieved 2.9 log inactivation of Escherichia coli at a delivery dose of 15 mJ/cm2. The results illustrate proof of concept that UV-C SEOFs can inactivate E. coli and should be further explored for delivering LED light into water.

Approaching easy water disinfection for all: Can in situ electrochlorination outperform conventional chlorination under realistic conditions?

Electrochlorination has gained research interest for its potential application as decentralized water treatment. A number of studies have displayed promising efficiency for water disinfection. However, a comprehensive comparison of in situ electrodisinfection to existing disinfection techniques, particularly under realistic water composition and flow rates, still needs additional research efforts. The aim of this study is to evaluate in situ electrochlorination while comparing the treatment with conventional chemical chlorination for point-of-entry decentralized disinfection at the household level. An electrochemical flow cell reactor was operated in a single pass mode considering water flow and water consumption for a household of four family members. Disinfection efficiency assessment of both electrochemical and chemical chlorination was conducted using bacterial and viral surrogates, E. coli and MS2 bacteriophage. Furthermore, a techno-economic analysis was conducted, using the levelized cost of water, to compare two electrochemical chlorination scenarios (i.e., electrical grid energy use, and solar panel powered system) and benchmarked against the baseline treatment of chemical chlorination. The findings revealed increased inactivation efficiency of in situ electrochlorination over conventional chlorination (p-value < 0.05). The synergetic impact of radicals and chlorine, and/or contribution of high chlorine concentration at acidic pH near anode surface were identified as key factors that could enhance disinfection performance of in situ electrochlorination. The techno-economic analysis demonstrated that electrochemical treatment, when operated using renewable energy sources, is not only a more environmentally sustainable approach, but also emerges as a more economically feasible solution for decentralized water treatment application. The results highlight that in situ electrochlorination is a more advanced alternative to decentralized water chlorination. However, further fundamental research on products and by-products formation under various water matrices is required.

Comparative study on electro-regeneration of antibiotic-laden activated carbons in reverse osmosis concentrate.

Electro-regeneration is emerging as a new technique to regenerate spent carbon adsorbents through an electrochemical process. In this study, sequential adsorption and electro-regeneration of ciprofloxacin (CIP)-laden carbon were investigated using both pristine and iron (Fe)-doped F400 activated carbon in distilled, deionized (DI) water and reverse osmosis (RO) concentrate water. The impact of reactor flow rate and sequential adsorption/electro-regeneration cycles on the regeneration efficiency were also evaluated. The results indicate that the breakthrough points for both adsorbents in DI water, where 100 % of the CIP molecules were adsorbed, occurred at around 7,800 bed volumes (BVs). Conversely, electro-regeneration for both adsorbents, where 94 % of the CIP molecules were desorbed, took place at 380 BVs. The main distinction between the two activated carbons lies in the initial range of BVs (<400 BVs).Fe doping on F400 appears to enhance its surface selectivity for CIP uptake, which can easily diffuse into the meso/macropore regions of Fe-doped F400. In contrast, pristine F400, being highly microporous, necessitated more contact time to fill its high-energy sites, resulting in a higher affinity for CIP adsorption. Over the four sequential adsorption/electro-regeneration cycles in DI water, a similar regeneration efficiency was observed at 190 BVs. As the flow rate increased from 2 to 6 mL/min, the CIP uptake on pristine F400 decreased in DI water, calculating 138, 74 and 57 mg/g for flow rates of 2, 4, and 6 mL/min, respectively. When the RO concentrate water was compared with DI water, the pristine F400 quickly reached saturation due to pore blockage caused by organic matter in RO concentrate. During electro-regeneration, up to 100 % of adsorbed CIP molecules were desorbed at around 120 BVs in RO concentrate, which is 3X faster than DI water. The effectiveness of this technology can be enhanced by implementing continuous flow systems, thereby improving the overall efficiency of CIP removal in RO concentrate.

Electrocatalytic water treatment of per- and polyfluoroalkyl substances reduces adsorbable organofluorine and bioaccumulation potential.

Per- and polyfluoroalkyl substances (PFAS) are pervasive in industrial processes, eliciting public concern upon their release into municipal sewers or the environment. Removing PFAS from the environment has become an urgent need. However, because potential endpoints span from energy-intensive complete mineralization to partial PFAS transformation, understanding and developing metrics for evaluating PFAS treatment can be a challenge. The goal of this study was to evaluate and compare the effectiveness of electrocatalytic degradation of PFAS with boron-doped diamond (BDD) electrodes using four techniques: LC-MS/MS target analysis, fluoride ion (F-), adsorbable organofluorine (AOF), and bioaccumulation potential using lipid-bilayer partition (LBP) tests. After 3 hours of electrocatalysis, >99% perfluorooctanoic acid (PFOA) degradation was achieved and corresponded with 84% conversion to F-, which was substantial - though intentionally not complete - defluorination. For the same 3 hour treatment time, AOF and LBP coefficient were reduced by 95% and 83%, respectively. LBP's detection limit was 2 orders of magnitude higher than that of AOF, so the positive correlation observed between LBP and AOF (r = 0.86) suggests AOF's practical utility as a design metric for assessing bioaccumulation potential of various organofluorine transformation by-products.

Nanobubble applications in aquaculture industry for improving harvest yield, wastewater treatment, and disease control.

The ever-growing demand for aquaculture has led the industry to seek novel approaches for more sustainable practices. These attempts aim to increase aquaculture yield by increasing energy efficiency and decreasing footprint and chemical demand without compromising animal health. For this, emerging nanobubbles (NBs) aeration technology gained attention. NBs are gas-filled pockets suspended as sphere-like cavities (bulk NBs) or attached to surfaces (surface NBs) with diameters of <1 µm. Compared to macro and microbubbles, NBs have demonstrated unique characteristics such as long residence times in water, higher gas mass transfer efficiency, and hydroxyl radical production. This paper focuses on reviewing NB technology in aquaculture systems by summarizing and discussing uses and implications. Three focus areas were targeted to review the applicability and effects of NBs in aquaculture: (i) NBs aeration to improve the aquaculture harvest yield and subsequent wastewater treatment; (ii) NB application for inactivation of harmful microorganisms; and (iii) NBs for reducing oxidative stress and improving animal health. Thus, this study reviews the research studies published in the last 10 years in which air, oxygen, ozone, and hydrogen NBs were tested to improve gas mass transfer, wastewater treatment, and control of pathogenic microorganisms. The experimental results indicated that air and oxygen NBs yield significantly higher productivity, growth rate, total harvest, survival rate, and less oxygen consumption in fish and shrimp farming. Secondly, the application of air and ozone NBs demonstrated the ability of efficient pollutant degradation. Third, NB application demonstrated effective control of infectious bacteria and viruses, and thus increased fish survival, as well as different gene expression patterns that induce immune responses to infections. Reviewed studies lack robust comparative analyses of the efficacy of macro- and microbubble treatments. Also, potential health and safety implications, as well as economic feasibility through factors such as changes in capital infrastructure, routine maintenance and energy consumption need to be considered and evaluated in parallel to applicability. Therefore, even with a promising future, further studies are needed to confirm the benefits of NB treatment versus conventional aquaculture practices.

Electrochemical degradation of acetaminophen in urine matrices: Unraveling complexity and implications for realistic treatment strategies.

Urine has an intricate composition with high concentrations of organic compounds like urea, creatinine, and uric acid. Urine poses a formidable challenge for advanced effluent treatment processes following urine diversion strategies. Urine matrix complexity is heightened when dealing with pharmaceutical residues like acetaminophen (ACT) and metabolized pharmaceuticals. This work explores ACT degradation in synthetic, fresh real, and hydrolyzed real urines using electrochemical oxidation with a dimensional stable anode (DSA). Analyzing drug concentration (2.5 - 40 mg L-1) over 180 min at various current densities in fresh synthetic effluent revealed a noteworthy 75% removal at 48 mA cm-2. ACT degradation kinetics and that of the other organic components followed a pseudo-first-order reaction. Uric acid degradation competed with ACT degradation, whereas urea and creatinine possessed higher oxidation resistance. Fresh real urine presented the most challenging scenario for the electrochemical process. Whereas, hydrolyzed real urine achieved higher ACT removal than fresh synthetic urine. Carboxylic acids like acetic, tartaric, maleic, and oxalic were detected as main by-products. Inorganic ionic species nitrate, nitrite, and ammonium ions were released to the medium from N-containing organic compounds. These findings underscore the importance of considering urine composition complexities and provide significant advancements in strategies for efficiently addressing trace pharmaceutical contamination.

Electrochemical oxidation of surfactants as an essential step to enable greywater reuse.

The practical application of electrochemical oxidation technology for the removal of surfactants from greywater was evaluated using sodium dodecyl sulfate (SDS) as a model surfactant. Careful selection of electrocatalysts and optimization of operational parameters demonstrated effective SDS removal in treating a complex greywater matrix with energy consumption below 1 kWh g-1 COD (Chemical Oxygen Demand), paving the way for a more sustainable approach to achieving surfactant removal in greywater treatment when aiming for decentralized water reuse. Chromatographic techniques identified carboxylic acids as key byproducts prior to complete mineralization. These innovative approaches represent a novel pathway for harnessing electrochemical technologies within decentralized compact devices, offering a promising avenue for further advancements in this field.

Optimized bimetallic ratios for durable membrane catalyst-film reactors in treating nitrate-polluted water.

Nitrate contamination of surface and ground water is a significant global challenge. Most current treatment technologies separate nitrate from water, resulting in concentrated wastestreams that need to be managed. Membrane Catalyst-film Reactors (MCfR), which utilize in-situ produced nanocatalysts attached to hydrogen-gas-permeable hollow-fiber membranes, offer a promising alternative for denitrification without generating a concentrated wastestream. In hydrogen-based MCfRs, bimetallic nano-scale catalysts reduce nitrate to nitrite and then further to di-nitrogen or ammonium. This study first investigated how different molar ratios of indium-to-palladium (In:Pd) catalytic films influenced denitrification rates in batch-mode MCfRs. We evaluated eleven In-Pd bimetallic catalyst films, with In:Pd molar ratios from 0.0029 to 0.28. Nitrate-removal exhibited a volcano-shaped dependence on In content, with the highest nitrate removal (0.19 mgNO3--N-min-1 L-1) occurring at 0.045 mol In/mol Pd. Using MCfRs with the optimal In:Pd loading, we treated nitrate-spiked tap water in continuous-flow for >60 days. Nitrate removal and reduction occurred in three stages: substantial denitrification in the first stage, a decline in denitrification efficiency in the second stage, and stabilized denitrification in the third stage. Factors contributing to the slowdown of denitrification were: loss of Pd and In catalysts from the membrane surface and elevated pH due to hydroxide ion production. Sustained nitrate removal will require that these factors be mitigated.

Opportunities for in situ electro-regeneration of organic contaminant-laden carbonaceous adsorbents.

Adsorptive separation technologies have proven to be effective on organic contaminant removal in aqueous water. However, the breakthrough of contaminants is inevitable and can be at relatively low bed volumes, which makes the regeneration of spent adsorbents an urgent need. Electrochemically induced regeneration processes are given special attention and may provide ease of operation through in situ regeneration avoiding (i) removal and transport adsorbents, and (ii) avoiding use of hazardous chemicals (i.e., organic solvents, acids, or bases). Therefore, this review article critically evaluates the fundamental aspects of in situ electro-regeneration for spent carbons, and later discusses specific examples related to the treatment of emerging contaminants (such as per- and polyfluoroalkyl substances or PFAS). The fundamental concepts of electrochemically driven processes are comprehensively defined and addressed in terms of (i) adsorbent characteristics, (ii) contaminant properties, (iii) adsorption/regeneration driving operational parameters and conditions, and (iv) the competitive effects of water matrices. Additionally, future research needs and challenges to enhance understanding of in situ electro-regeneration applications for organic contaminants (specifically PFAS)-laden adsorbents are identified and outlined as a future key perspective.

Self-supported polypyrrole flexible electrodes for electrochemical reduction of nitrite.

The efficiency of an electrochemical oxidation/reduction process strongly depends on the working electrode's surface area to volume ratio. By making electrodes flexible and employing different configurations such as roll-to-roll membrane, the surface area to volume ratio can be enhanced, therefore improving the overall efficiency of electrochemical processes. Conductive polymers emerge as a new framework to enable alternative electrochemical water treatment cell configurations. Self-standing polypyrrole flexible electrodes were synthesized by electropolymerization and evaluated on the treatment of an oxyanion pollutant: nitrite. Mechanical characterization through stress-strain curves and bending tests demonstrated high electrode resilience that sustained over 1000 bending cycles without impacting mechanical integrity or electrocatalytic responses. The electrocatalytic response towards nitrite reduction was assessed under linear scan voltammetry (LSV) and removal performance evaluated under potentiostatic conditions reaching 79% abatement of initial concentrations of nitrite of 15 mg/L [NO2--N]. Self-standing flexible electrodes appear as a novel framework to enable modular compact water treatment unit designs that maximize the electrode area/volume ratio and substitute expensive platinum group metal (PGMs) electrocatalysts.