Energetic Comparison of Flow-Electrode Capacitive Deionization and Membrane Technology: Assessment on Applicability in Desalination Fields.

Flow-electrode capacitive deionization (FCDI) is a promising technology for sustainable water treatment. However, studies on the process have thus far been limited to lab-scale conditions and select fields of application. Such limitation is induced by several shortcomings, one of which is the absence of a comprehensive process model that accurately predicts the operational performance and the energy consumption of FCDI. In this study, a simulation model is newly proposed with initial validation based on experimental data and is then utilized to elucidate the performance and the specific energy consumption (SEC) of FCDI under multiple source water conditions ranging from near-groundwater to high salinity brine. Further, simulated pilot-scale FCDI system was compared with actual brackish water reverse osmosis (BWRO) and seawater reverse osmosis (SWRO) plant data with regard to SEC to determine the feasibility of FCDI as an alternative to the conventional membrane processes. Analysis showed that FCDI is competent for operation against brackish water solutions under all possible operational conditions with respect to the BWRO. Moreover, its distinction can be extended to the SWRO for seawater conditions through optimization of its total effective membrane area via scale-up. Accordingly, future directions for the advancement of FCDI was suggested to ultimately prompt the commercialization of the FCDI process.

Harnessing the potential of in-situ, electrically generated microbubbles via nickel foam for enhanced, low energy membrane fouling control.

For membrane-based, water treatment technologies, fouling remains a significant challenge for pressure-driven processes. While many antifouling strategies have been proposed, there remains significant room for improved efficiency. Direct application of microbubbles (MBs) at a membrane surface offers a promising approach for managing interfacial fouling through continuous physical interaction(s). Despite such potential, to date, integration and optimization of in-situ generated MBs at the membrane interface that are both highly antifouling with minimal energy inputs and unwanted side reactions remains mostly outstanding. Here we demonstrate the application of conductive, porous nickel foam for electrolysis-based generation of hydrogen microbubbles at an ultra-filtration (UF) membrane interface, which significantly mitigates membrane fouling for a range of model foulants. System characterization and optimization includes comparison of metal foams (Ni, Cu, Ti), faradic efficiencies, hydrogen evolution reaction (HER) curves, cyclic voltammetry, and quantification of hydrogen gas flux and bubble size, as a function of applied current. When optimized, we report rapid (<5 min) and near complete (∼99 %) flux recovery for three classes of foulants, including calcium alginate, humic acid (HA), and SiO2 particles. For all, the described MB-based approach is orders of magnitude more energy efficient when compared to conventional cleaning strategies. Finally, we demonstrate the MB-based regeneration/cleaning process is stable and repeatable for ten cycles and also highly effective for a challenge water (as a model oilfield brine). Taken together, this work presents a novel and efficient approach for the application of in-situ electrically generated MBs to support sustainable pressure-driven membrane processes.

Advancements of remote data acquisition and processing in unmanned vehicle technologies for water quality monitoring: An extensive review.

Regular water quality monitoring is becoming desirable due to the increase in water pollution caused by both climate change and the generation of industrial chemicals. Unmanned vehicles have emerged as key technologies for remote data acquisition, providing fast and accurate methods for water quality monitoring. However, current research on unmanned vehicles has not systematically examined their features and limitations, which are crucial for identifying future research directions and applications of unmanned vehicle technologies. Therefore, this study extensively reviews the advancements in remote data acquisition and processing using unmanned vehicle technologies for water quality monitoring to provide valuable insights for future research. First, the types of unmanned vehicles and their application ranges for water quality monitoring are summarized. Among the unmanned vehicle technologies, unmanned aerial vehicles are considered primary platforms for water quality monitoring due to their wide data acquisition range and their ability to accommodate diverse sensors and samplers. Also, the types of samplers and sensors mounted on the unmanned vehicles are analyzed based on their characteristics. It is concluded that spectral sensors offer the most cost-effective approach for acquiring real-time water quality data. Furthermore, algorithms that convert image data into water quality data are examined, focusing on data preprocessing, analysis, and validation. The findings reveal a close relationship between the analysis of spectral characteristics of each water quality parameter and the wavelength ranges of red and red-edge. Lastly, future research directions for unmanned vehicle technologies are further suggested based on the summarized technological limitations.

Electrically conductive membrane distillation via an alternating current operation for zero liquid discharge.

Membrane distillation (MD) shows promise for achieving high salinity treatment and zero liquid discharge (ZLD) compared to conventional water treatment processes due to its unique characteristics, including low energy consumption and high resulting water quality. However, performance degradation due to fouling and scaling under high recovery conditions remains a challenge, particularly considering the need to control both cations and anions for maximum scaling mitigation. Accordingly, in this study, alternating current (AC) operation for electrically conductive membrane distillation (ECMD) is newly proposed, based on its potential for controlling both cations and anions, in contrast to conventional direct current (DC) operation. Systematic experiments and theoretical analysis show that water recovery in ECMD can be increased by 27% through AC operation. The proposed modification and effective AC operation of ECMD increase the practicality of using MD in desalination for a high recovery rate, perhaps even for ZLD.

Feasibility study of storing CO2 in the ocean by marine environmental impact assessment.

Since the industrial revolution, which was accompanied with the use of fossil fuels as an energy source, the content of carbon dioxide (CO2) in the atmosphere has increased. To mitigate global warming, industries that utilize fossil fuels have continuously explored new approaches to reduce CO2 emissions and convert it to alternative fuels. The ocean is a vast source of absorbed CO2 on Earth, and various studies have been conducted on the use of the ocean to reduce global CO2. This study focused on reducing CO2 in the atmosphere by storing it as bicarbonate, a form of CO2 that exists in the ocean. The optimum condition for the conversion of CO2 into bicarbonate was investigated by considering the dissolved inorganic carbon (DIC; HCO3-, CO32-, H2CO3) concentration and pH. To confirm the biological impact of this conversion, biological impact experiments were conducted under various DIC concentrations using Skeletonema japonicum, a phytoplankton present in most areas of the sea. Based on the DIC concentration (2.09 mM) of the seawater, the DIC concentrations used in the Lab-scale experiment ranged from 2.5 mM to 18.75 mM, and the concentration with the highest conversion rate (< 6.38 mM) was applied in the pilot plant. Marine environmental impact modeling was performed to observe the effect of discharge to the ocean and its movement. The results revealed a slight growth inhibition of phytoplankton at DIC concentrations higher than the base concentration. Nevertheless, the change in the DIC concentration exerted no effect on the phytoplankton growth except at extremely high concentrations. Moreover, the high DIC concentration can be diluted by the ocean current flow rate, thus counterbalancing the growth inhibition effect. The results obtained in this study demonstrate the feasibility of CO2 storage in the form of DIC, and will be helpful for further development of CO2 mitigation.

Ultraviolet light-activated peroxymonosulfate (UV/PMS) system for humic acid mineralization: Effects of ionic matrix and feasible application in seawater reverse osmosis desalination.

The use of membrane-based technology has evolved into an important strategy for supplying freshwater from seawater and wastewater to overcome the problems of water scarcity around the world. However, the presence of natural organic matter (NOM), including humic substances affects the performance of the process. Here, we present a systematic report on the mineralization of humic acid (HA), as a model for NOM, in high concentration of salts using the ultraviolet light-activated peroxymonosulfate (UV/PMS) system as a potential alternative for HA elimination during membrane-based seawater desalination and water treatment processes. Effects of various parameters such as PMS concentration, solution type, pH, anions, and anion-cation matrix on HA mineralization were assessed. The results show that 100%, 78% and 58% of HA (2 mg/L TOC) were mineralized with rate constants of 0.085 min-1, 0.0073 min-1, and 0.0041 min-1 after 180 min reaction time at pH 7 when 0.5 mM PMS was used in deionized water, sodium chloride solution (35,000 ppm) and synthetic seawater, respectively. The reduced efficiency under saline conditions was attributed to the presence of anions in the system that acted as sulfate and hydroxyl radicals' scavengers. Furthermore, the safety of the treated synthetic seawater was evaluated by analyzing the residual transformed products. Overall, pretreatment with the UV/PMS system mitigated fouling on the RO membrane.

Electrode for selective bromide removal in membrane capacitive deionisation.

Due to the shortage of freshwater around the world, seawater is becoming an important water source. However, seawater contains a high concentration of bromide that can form harmful disinfection by-products during water disinfection. Therefore, the current seawater reverse osmosis (SWRO) has to adopt two-pass reverse osmosis (RO) configuration for effective bromide removal, increasing the overall desalination cost. In this study, a bromide selective composite electrode was developed for membrane capacitive deionisation (MCDI). The composite electrode was developed by coating a mixture of bromide selective resin and anion exchange polymer on the surface of the commercial activated carbon electrode, and its performance was compared to that of conventional carbon electrode. The results demonstrated that the composite electrode has ten times better bromide selectivity than the conventional carbon electrode. The study shows the potential application of MCDI for the selective removal of target ions from water sources and the potential for resource recovery through basic modification of commercial electrode.

Chloride-Mediated Enhancement in Heat-Induced Activation of Peroxymonosulfate: New Reaction Pathways for Oxidizing Radical Production.

This study is the first to demonstrate the capability of Cl- to markedly accelerate organic oxidation using thermally activated peroxymonosulfate (PMS) under acidic conditions. The treatment efficiency gain allowed heat-activated PMS to surpass heat-activated peroxydisulfate (PDS). During thermal PMS activation at excess Cl-, accelerated oxidation of 4-chlorophenol (susceptible to oxidation by hypochlorous acid (HOCl)) was observed along with significant degradation of benzoic acid and ClO3- occurrence, which involved oxidants with low substrate specificity. This indicated that heat facilitated HOCl formation via nucleophilic Cl- addition to PMS and enabled free chlorine conversion into less selective oxidizing radicals. HOCl acted as a key intermediate in the major oxidant transition based on temperature-dependent variation in HOCl concentration profiles, kinetically retarded organic oxidation upon NH4+ addition, and enabled rapid organic oxidation in heated PMS/HOCl mixtures. Chlorine atom that formed via the one-electron oxidation of Cl- by the sulfate radical served as the primary oxidant and was involved in hydroxyl radical production. This was corroborated by the quenching effects of alcohols and bicarbonates, reactivity toward multiple organics, and electron paramagnetic resonance spectral features. PMS outperformed PDS in degrading benzoic acid during thermal activation operated in reverse osmosis concentrate, which was in conflict with the well-established superiority of heat-activated PDS.

Retardation of wetting for membrane distillation by adjusting major components of seawater.

Wetting by fouling is phenomenon specific to membrane distillation (MD) and are regarded as challenges to the seawater membrane distillation (SWMD) process. To understand fouling and wetting, the influence of Mg and Sr crystals, which can potentially cause scaling, as well as Ca crystals deposited on the membrane surface were investigated. Mg(OH)2 and CaSO4 had significant impact on fouling and wetting. Even if CaCO3 and SrSO4 had no effects on fouling and wetting as single salts, CaCO3 and CaSO4 were dominant in synthetic seawater without Mg(OH)2. However, the occurrence of Mg(OH)2 scales became a cause for concern if Ca ion was removed from seawater for the prevention of fouling and wetting. Therefore, Mg as well as Ca should be removed for proper fouling and wetting control. NaOH/Na2CO3 softening was used for the removal of Ca and Mg ions. In addition, based on the inhibition effects of Mg ions on Ca scales, a new pretreatment method involving the injection of MgCl2 to increase the Mg /Ca ratio was examined.

Electrochemical Oxidation-Membrane Distillation Hybrid Process: Utilizing Electric Resistance Heating for Distillation and Membrane Defouling through Thermal Activation of Anodically Formed Persulfate.

This study reports distillation-based salt removal by Ohmic heating in a hybrid process, in which electrochemical oxidation (EO) and direct contact membrane distillation (DCMD) are performed sequentially. In addition to anodically destructing the organics, the hybrid process also separated the sulfate-based electrolytes from treated water through distillation, without consuming external energy, owing to the temperature of the aqueous sulfate solution being elevated to 70 °C via resistive heating. The hybrid process treated organic compounds in a nonselective fashion, whereas DCMD alone did not completely reject (semi)volatile organics. Integrating EO with DCMD made the hybrid process resistant toward the wetting phenomenon; the process exhibited a steady distillate flux and salt rejection as the initial loading of amphiphilic sodium dodecyl sulfate was increased to 0.3 mM. Anodic persulfate formation from the sulfate and Ohmic heating caused an in situ yield of the sulfate radical in the feed solution; this eliminated membrane fouling, according to the observation that the water flux, which was drastically reduced upon adding alginate, was recovered immediately after an electric current was applied. The hybrid process concurrently decomposed spiked organics and removed naturally present inorganic ions in actual flue gas desulfurization wastewater, without an external supply of electrolyte and heat energy.

Comprehensive analysis of a hybrid FO/crystallization/RO process for improving its economic feasibility to seawater desalination.

In this study, the FO/crystallization/RO hybrid process was analyzed comprehensively, including experimentation, modeling, and energy and cost estimation, to examine and improve its feasibility to seawater desalination. A new operating strategy by heating the FO process to 45 °C was suggested, and a detailed process design was conducted. A comparative analysis with the conventional seawater reverse osmosis (SWRO) process was performed in terms of specific energy consumption (SEC) and specific water cost (SWC). The hybrid process can produce fresh water with SWC of 0.6964 $/m3, electrical SEC of 2.71 kWh/m3, and thermal SEC of 14.684 kWh/m3. Compared to the conventional SWRO process (SWC of 0.6890 $/m3 and electrical SEC of 2.674 kWh/m3), the hybrid process can produce water with comparable cost and energy consumption. An economic feasibility study that utilized the waste heat and the developed FO technology was also carried out to investigate future developments of the hybrid process. The SWC can be reduced to 0.6435 $/m3 with free waste heat energy. The permeate water quality of the hybrid process was about half that of the conventional SWRO process on molar basis. The results revealed that the FO/crystallization/RO hybrid process can be utilized as a competitive process for seawater desalination with high recovery and high water quality.

Bromide and iodide selectivity in membrane capacitive deionisation, and its potential application to reduce the formation of disinfection by-products in water treatment.

The formation of toxic disinfection by-products during water disinfection due to the presence of bromide and iodide is a major concern. Current treatment technologies such as membrane, adsorption and electrochemical processes have been known to have limitations such as high energy demand and excessive chemical use. In this study, the selectivity between bromide and iodide, and their removal in membrane capacitive deionisation (MCDI) was evaluated. The results showed that iodide was more selectively removed over bromide from several binary feed waters containing bromide and iodide under various initial concentrations and applied voltages. Even in the presence of significant background concentration of sodium chloride, definite selectivity of iodide over bromide was observed. The high partial-charge transfer coefficient of iodide compared to bromide could be a feasible explanation for high iodide selectivity since both bromide and iodide have similar ionic charge and hydrated radius. The result also shows that MCDI can be a potential alternative for the removal of bromide and iodide during water treatment.

Relating Organic Fouling in Membrane Distillation to Intermolecular Adhesion Forces and Interfacial Surface Energies.

This study investigates the fouling mechanisms in membrane distillation, focusing on the impact of foulant type and membrane surface chemistry. Interaction forces between a surface-functionalized particle probe simulating a range of organic foulants and model surfaces, modified with different surface energy materials, were measured by atomic force microscopy. The measured interaction forces were compared to those calculated based on the experimentally determined surface energy components of the particle probe, model surface, and medium (i.e., water). Surfaces with low interfacial energy exhibited high attractive interaction forces with organic foulants, implying a higher fouling potential. In contrast, hydrophilic surfaces (i.e., surfaces with high interfacial energy) showed the lowest attractive forces with all types of foulants. We further performed fouling experiments with alginate, humic acid, and mineral oil in direct contact membrane distillation using polyvinylidene fluoride membranes modified with various materials to control membrane surface energy. The observed fouling behavior was compared to the interaction force data to better understand the underlying fouling mechanisms. A remarkable correlation was obtained between the evaluated interaction force data and the fouling behavior of the membranes with different surface energy. Membranes with low surface energy were fouled by hydrophobic, low surface tension foulants via "attractive" and subsequent "adsorptive" interaction mechanisms. Furthermore, such membranes have a higher fouling potential than membranes with high or ultralow surface energy.

Treatment of industrial wastewater produced by desulfurization process in a coal-fired power plant via FO-MD hybrid process.

In this study, the feasibility of forward osmosis (FO) hybridized with membrane distillation (MD) was systematically investigated for treating flue gas desulfurization (FGD) wastewater. FO experiments were conducted using raw FGD wastewater obtained from a coal-fired power plant in Korea. Severe membrane fouling in FO was observed since FGD wastewater contained various components (i.e., particles, colloids, organics, and ions). The combined fouling layer by particulates and scales was identified via scanning electron microscope (SEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD). Therefore, fouling control strategies were suggested and evaluated. Microfiltration (MF) pre-treatment was effective in removing particulates and mitigating the initial fouling. Antiscalant-blended draw solution (DS) could inhibit the formation of membrane scaling. With such fouling control schemes, FO achieved the highest recovery rate compared to other desalting processes (i.e., RO and MD), suggesting that FO is suitable for treating wastewater with high fouling potential and high TDS. Finally, the diluted DS was recovered by MD. MD could re-concentrate the diluted DS up to 50% recovery rate with no significant flux decline. Rapid flux decline was then observed due to membrane scaling. Thus, appropriate antiscalants in DS should be considered to inhibit scaling formation in FO and MD simultaneously.

Understanding possible underlying mechanism in declining germicidal efficiency of UV-LED reactor.

Since ultraviolet light emitting diodes (UV-LEDs) have emerged as an alternative light source for UV disinfection systems, enhancement of reactor performance is a demanding challenge to promote its practical application in water treatment process. This study explored the underlying mechanism of the inefficiency observed in flow-through mode UV disinfection tests to improve the light utilization of UV-LED applications. In particular, the disinfection performance of UV-LED reactors was evaluated using two different flow channel types, reservoir and pathway systems, in order to elucidate the impact of physical circumstances on germicidal efficiency as the light profile was adjusted. Overall, a significant reduction in germicidal efficiency was observed when exposure time was prolonged or a mixing chamber was integrated. Zeta analysis revealed that the repulsion rate between microorganisms decreased with UV fluence transfer, and that change might cause the shielding effect of UV delivery to target microorganisms. In line with the above findings, the reduction in efficiency intensified when opportunities for microbial collision increased. Thus, UV induced microbial aggregation was implicated as being a disinfection hindering factor, exerting its effect through uneven UV illumination. Ultimately, the results refuted the prevailing belief that UV has a cumulative effect. We found that the reservoir system achieved worse performance than the pathway system despite it providing 15 times higher UV fluence: the differences in germicidal efficiency were 1-log, 1.4-log and 1.7-log in the cases of P.aeruginosa, E.coli and S.aureus, respectively.

Mesoporous carbon for efficient removal of microcystin-LR in drinking water sources, Nak-Dong River, South Korea: Application to a field-scale drinking water treatment plant.

Microcystin-LR (MC-LR) is a growing issue as it is toxic and difficult to remove in drinking water treatment plants (DWTPs). Mesoporous carbon (MC) is evaluated as an alternative adsorbent for MC-LR removal and compared with three widely-used powdered activated carbons (PACs). MC was more favorable for MC-LR removal than PACs. MC-LR adsorption on MC was a rapid process (k2 = 1.02  ×  10-4 g/µg/min) that completed within 15 min, while adsorption on PACs took 60 min. The maximum adsorption capacity of MC-LR was 18,008 µg/g (MC), which was higher than that of the PACs. Two mechanisms were associated with adsorption: the small hydro-dynamic diameter of MC in an aqueous solution increased the instantaneous attraction of MC-LR to its surface, and the numerous mesopores enhanced pore diffusion. The MC could remove MC-LR to meet the drinking water guidance level (1 µg/L) from an the MC-LR concentration range of 5-20 µg/L in drinking water sources, and 10 min of treatment was sufficient to meet this level (MC dose = 20 mg/L). The field-scale DWTP was operated by adding 1 or 5 mg/L MC to the mixing basin, and 49.49% and 74.50% of MC-LR was removed, respectively. Geosmin and 2-methylisoborneol were slightly reduced when 5 mg/L of MC was applied.

Recovery of water and minerals from shale gas produced water by membrane distillation crystallization.

Shale gas produced water (SGPW) treatment imposes greater technical challenges because of its high concentration of various contaminants. Membrane distillation crystallization (MDC) has a great potential to manage SGPW since it is capable of recovering both water and minerals at high rates, up to near a zero liquid discharge (ZLD) condition. To evaluate the feasibility of MDC for SGPW treatment, MDC performance indicators, such as water recovery rate, solid production rate (SPR) and specific energy consumption (SEC), were systematically investigated, to our knowledge for the first time, by using actual SGPW from Eagle Ford Shale (USA). The main operating parameters including feed cross-flow velocity (CFV) and crystallization temperature (TCr) were optimized by performing a series of MDC experiments. The results reported that water and minerals were effectively recovered with 84% of recovery rate and 2.72 kg/m2day of SPR under respective optimal operating conditions. Furthermore, the scale mechanism was firstly identified as limiting factor for MDC performance degradation. Lastly, SEC of MDC was estimated to be as low as 28.2 kWh/m3 under ideal optimal operating conditions. Our experimental observations demonstrated that MDC could sustainably and effectively recover water and mineral with low energy consumption from SGPW by optimizing operating condition.

Nanoscale Pillar-Enhanced Tribological Surfaces as Antifouling Membranes.

We present a nonconventional membrane surface modification approach that utilizes surface topography to manipulate the tribology of foulant accumulation on water desalination membranes via imprinting of submicron titanium dioxide (TiO2) pillar patterns onto the molecularly structured, flat membrane surface. This versatile approach overcomes the constraint of the conventional approach relying on interfacial polymerization that inevitably leads to the formation of ill-defined surface topography. Compared to the nonpatterned membranes, the patterned membranes showed significantly improved fouling resistance for both organic protein and bacterial foulants. The use of hydrophilic TiO2 as a pattern material increases the membrane hydrophilicity, imparting improved chemical antifouling resistance to the membrane. Fouling behavior was also interpreted in terms of the topographical effect depending on the relative size of foulants to the pattern dimension. In addition, computational fluid dynamics simulation suggests that the enhanced antifouling of the patterned membrane is attributed to the enhancement in overall and local shear stress at the fluid-TiO2 pattern interface.

Evaluation of poly (aspartic acid sodium salt) as a draw solute for forward osmosis.

Poly (aspartic acid sodium salt) (PAspNa) was evaluated for its potential as a novel draw solute in forward osmosis (FO). The inherent advantages of PAspNa, such as good water solubility, high osmotic pressure, and nontoxicity, were first examined through a series of physicochemical analyses and atomic-scale molecular dynamics simulations. Then, lab-scale FO tests were performed to evaluate its suitability in practical processes. Compared to other conventional inorganic solutes, PAspNa showed comparable water flux but significantly lower reverse solute flux, demonstrating its suitability as a draw solute. Moreover, fouling experiments using synthetic wastewater as a feed solution demonstrated that PAspNa reversely flowed to the feed side reduced inorganic scaling on the membrane active layer. The recyclability of PAspNa was studied using both nanofiltration (NF) and membrane distillation (MD) processes, and the results exhibited its ease of recovery. This research reported the feasibility and applicability of FO-NF or FO-MD processes using PAspNa for wastewater reclamation and brackish water desalination.

Fouling distribution in forward osmosis membrane process.

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis (FO) membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic (alginate) fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter-current flow operation of FO membrane process.