Reverse Osmosis Biofilm Dispersal by Osmotic Back-Flushing: Cleaning via Substratum Perforation

We have demonstrated the application of osmotic back-flushing (OBF) for the removal of biofilms from reverse osmosis (RO) membranes and proposed a new biofilm dispersal mechanism. OBF was conducted in a laboratory-scale RO test cell by introducing a sequence of hypersaline solution (1.5 M NaCl) flushes into the feedwater, while still maintaining the applied hydraulic pressure (13.8 bar). OBF resulted in significant biofilm detachment, leaving a thin, perforated bacterial film (24 μm thickness) with vertical cavities ranging from 15 to 50 μm in diameter. Application of OBF led to significant reductionin the biovolume (70–79%) and substantial removal of total organic carbon and proteins (78 and 66%, respectively), resulting in 63% permeate water flux recovery. Our findings demonstrate the potential of this chemical-free RO membrane cleaning method while highlighting the possible challenges of the technique

Comparison of Energy Efficiency and Power Density in Pressure Retarded Osmosis and Reverse Electrodialysis

Pressure retarded osmosis (PRO) and reverse electrodialysis (RED) are emerging membrane-based technologies that can convert chemical energy in salinity gradients to useful work. The two processes have intrinsically different working principles: controlled mixing in PRO is achieved by water permeation across salt-rejecting membranes, whereas RED is driven by ion flux across charged membranes. This study compares the energy efficiency and power density performance of PRO and RED with simulated technologically available membranes for natural, anthropogenic, and engineered salinity gradients (seawater–river water, desalination brine–wastewater, and synthetic hypersaline solutions, respectively). The analysis shows that PRO can achieve both greater efficiencies (54–56%) and higher power densities (2.4–38 W/m²) than RED (18–38% and 0.77–1.2 W/m²). The superior efficiency is attributed to the ability of PRO membranes to more effectively utilize the salinity difference to drive water permeation and better suppress the detrimental leakage of salts. On the other hand, the low conductivity of currently available ion exchange membranes impedes RED ion flux and, thus, constrains the power density. Both technologies exhibit a trade-off between efficiency and power density: employing more permeable but less selective membranes can enhance the power density, but undesired entropy production due to uncontrolled mixing increases and some efficiency is sacrificed. When the concentration difference is increased (i.e., natural → anthropogenic → engineered salinity gradients), PRO osmotic pressure difference rises proportionally but not so for RED Nernst potential, which has logarithmic dependence on the solution concentration. Because of this inherently different characteristic, RED is unable to take advantage of larger salinity gradients, whereas PRO power density is considerably enhanced. Additionally, high solution concentrations suppress the Donnan exclusion effect of the charged RED membranes, severely reducing the permselectivity and diminishing the energy conversion efficiency. This study indicates that PRO is more suitable to extract energy from a range of salinity gradients, while significant advancements in ion exchange membranes are likely necessary for RED to be competitive with PRO

Thermodynamic and Energy Efficiency Analysis of Power Generation from Natural Salinity Gradients by Pressure Retarded Osmosis

The Gibbs free energy of mixing dissipated when fresh river water flows into the sea can be harnessed for sustainable power generation. Pressure retarded osmosis (PRO) is one of the methods proposed to generate power from natural salinity gradients. In this study, we carry out a thermodynamic and energy efficiency analysis of PRO work extraction. First, we present a reversible thermodynamic model for PRO and verify that the theoretical maximum extractable work in a reversible PRO process is identical to the Gibbs free energy of mixing. Work extraction in an irreversible constant-pressure PRO process is then examined. We derive an expression for the maximum extractable work in a constant-pressure PRO process and show that it is less than the ideal work (i.e., Gibbs free energy of mixing) due to inefficiencies intrinsic to the process. These inherent inefficiencies are attributed to (i) frictional losses required to overcome hydraulic resistance and drive water permeation and (ii) unutilized energy due to the discontinuation of water permeation when the osmotic pressure difference becomes equal to the applied hydraulic pressure. The highest extractable work in constant-pressure PRO with a seawater draw solution and river water feed solution is 0.75 kWh/m³ while the free energy of mixing is 0.81 kWh/m³a thermodynamic extraction efficiency of 91.1%. Our analysis further reveals that the operational objective to achieve high power density in a practical PRO process is inconsistent with the goal of maximum energy extraction. This study demonstrates thermodynamic and energetic approaches for PRO and offers insights on actual energy accessible for utilization in PRO power generation through salinity gradients

Adverse Impact of Feed Channel Spacers on the Performance of Pressure Retarded Osmosis

This article analyzes the influence of feed channel spacers on the performance of pressure retarded osmosis (PRO). Unlike forward osmosis (FO), an important feature of PRO is the application of hydraulic pressure on the high salinity (draw solution) side to retard the permeating flow for energy conversion. We report the first observation of membrane deformation under the action of the high hydraulic pressure on the feed channel spacer and the resulting impact on membrane performance. Because of this observation, reverse osmosis and FO tests that are commonly used for measuring membrane transport properties (water and salt permeability coefficients, <i>A</i> and <i>B</i>, respectively) and the structural parameter (<i>S</i>) can no longer be considered appropriate for use in PRO analysis. To accurately predict the water flux as a function of applied hydraulic pressure difference and the resulting power density in PRO, we introduced a new experimental protocol that accounts for membrane deformation in a spacer-filled channel to determine the membrane properties (<i>A</i>,<i> B</i>, and <i>S</i>). PRO performance model predictions based on these determined <i>A</i>, <i>B</i>, and <i>S</i> values closely matched experimental data over a range of draw solution concentrations (0.5 to 2 M NaCl). We also showed that at high pressures feed spacers block the permeation of water through the membrane area in contact with the spacer, a phenomenon that we term the shadow effect, thereby reducing overall water flux. The implications of the results for power generation by PRO are evaluated and discussed

Influence of Natural Organic Matter Fouling and Osmotic Backwash on Pressure Retarded Osmosis Energy Production from Natural Salinity Gradients

Pressure retarded osmosis (PRO) has the potential to produce clean, renewable energy from natural salinity gradients. However, membrane fouling can lead to diminished water flux productivity, thus reducing the extractable energy. This study investigates organic fouling and osmotic backwash cleaning in PRO and the resulting impact on projected power generation. Fabricated thin-film composite membranes were fouled with model river water containing natural organic matter. The water permeation carried foulants from the feed river water into the membrane porous support layer and caused severe water flux decline of ∼46%. Analysis of the water flux behavior revealed three phases in membrane support layer fouling. Initial foulants of the first fouling phase quickly adsorbed at the active-support layer interface and caused a significantly greater increase in hydraulic resistance than the subsequent second and third phase foulants. The water permeability of the fouled membranes was lowered by ∼39%, causing ∼26% decrease in projected power density. A brief, chemical-free osmotic backwash was demonstrated to be effective in removing foulants from the porous support layer, achieving ∼44% recovery in projected power density. The substantial performance recovery after cleaning was attributed to the partial restoration of the membrane water permeability. This study shows that membrane fouling detrimentally impacts energy production, and highlights the potential strategies to mitigate fouling in PRO power generation with natural salinity gradients

Omniphobic Polyvinylidene Fluoride (PVDF) Membrane for Desalination of Shale Gas Produced Water by Membrane Distillation

Microporous membranes fabricated from hydrophobic polymers such as polyvinylidene fluoride (PVDF) have been widely used for membrane distillation (MD). However, hydrophobic MD membranes are prone to wetting by low surface tension substances, thereby limiting their use in treating challenging industrial wastewaters, such as shale gas produced water. In this study, we present a facile and scalable approach for the fabrication of omniphobic polyvinylidene fluoride (PVDF) membranes that repel both water and oil. Positive surface charge was imparted to an alkaline-treated PVDF membrane by aminosilane functionalization, which enabled irreversible binding of negatively charged silica nanoparticles (SiNPs) to the membrane through electrostatic attraction. The membrane with grafted SiNPs was then coated with fluoroalkylsilane (perfluorodecyltrichlorosilane) to lower the membrane surface energy. Results from contact angle measurements with mineral oil and surfactant solution demonstrated that overlaying SiNPs with ultralow surface energy significantly enhanced the wetting resistance of the membrane against low surface tension liquids. We also evaluated desalination performance of the modified membrane in direct contact membrane distillation with a synthetic wastewater containing surfactant (sodium dodecyl sulfate) and mineral oil, as well as with shale gas produced water. The omniphobic membrane exhibited a stable MD performance, demonstrating its potential application for desalination of challenging industrial wastewaters containing diverse low surface tension contaminants

The Critical Need for Increased Selectivity, Not Increased Water Permeability, for Desalination Membranes

Desalination membranes are essential for the treatment of unconventional water sources, such as seawater and wastewater, to alleviate water scarcity. Promising research efforts on novel membrane materials may yield significant performance gains over state-of-the-art thin-film composite (TFC) membranes, which are constrained by the permeability–selectivity trade-off. However, little guidance currently exists on the practical impact of such performance gains, namely enhanced water permeability or enhanced water–solute selectivity. In this critical review, we first discuss the performance of current TFC membranes. We then highlight and provide context for recent module-scale modeling studies that have found limited impact of increased water permeability on the efficiency of desalination processes. Next we cover several important examples of water treatment processes in which inadequate membrane selectivity hinders process efficacy. We conclude with a brief discussion of how the need for enhanced selectivity may influence the design strategies of future membranes

Elucidating the Role of Oxidative Debris in the Antimicrobial Properties of Graphene Oxide

In this paper, we investigate, for the first time, how oxidative debris affects the antimicrobial activity of graphene oxide (GO). Besides the conventional definition of GO structure, our study demonstrates that GO is also composed of one additional component called oxidative debris, small and highly oxidized fragments adsorbed on the GO surface. After the removal of oxidative debris using an alkaline washing process, the toxicity of GO sheets to <i>Escherichia coli</i> cells significantly decreased. Raman spectroscopy measurements and acellular oxidation of glutathione indicated that oxidative debris increase the antimicrobial activity of GO sheets by improving their ability to promote bacteria inactivation via cell membrane damage and oxidative stress mechanisms. Given the influence of oxidative debris on the antimicrobial activity of GO, our findings emphasize the need to investigate the presence of oxidative debris before establishing correlations between physicochemical properties and the bioreactivity of GO sheets

Module-Scale Analysis of Pressure Retarded Osmosis: Performance Limitations and Implications for Full-Scale Operation

We investigate the performance of pressure retarded osmosis (PRO) at the module scale, accounting for the detrimental effects of reverse salt flux, internal concentration polarization, and external concentration polarization. Our analysis offers insights on optimization of three critical operation and design parametersapplied hydraulic pressure, initial feed flow rate fraction, and membrane areato maximize the specific energy and power density extractable in the system. For co- and counter-current flow modules, we determine that appropriate selection of the membrane area is critical to obtain a high specific energy. Furthermore, we find that the optimal operating conditions in a realistic module can be reasonably approximated using established optima for an ideal system (i.e., an applied hydraulic pressure equal to approximately half the osmotic pressure difference and an initial feed flow rate fraction that provides equal amounts of feed and draw solutions). For a system in counter-current operation with a river water (0.015 M NaCl) and seawater (0.6 M NaCl) solution pairing, the maximum specific energy obtainable using performance properties of commercially available membranes was determined to be 0.147 kWh per m³ of total mixed solution, which is 57% of the Gibbs free energy of mixing. Operating to obtain a high specific energy, however, results in very low power densities (less than 2 W/m²), indicating that the trade-off between power density and specific energy is an inherent challenge to full-scale PRO systems. Finally, we quantify additional losses and energetic costs in the PRO system, which further reduce the net specific energy and indicate serious challenges in extracting net energy in PRO with river water and seawater solution pairings

Electrochemical Carbon-Nanotube Filter Performance toward Virus Removal and Inactivation in the Presence of Natural Organic Matter

The performance of an electrochemical multiwalled carbon nanotube (EC-MWNT) filter toward virus removal and inactivation in the presence of natural organic matter was systematically evaluated over a wide range of solution chemistries. Viral removal and inactivation were markedly enhanced by applying DC voltage in the presence of alginate and Suwannee River natural organic matter (SRNOM). Application of 2 or 3 V resulted in complete (5.8 to 7.4 log) removal and significant inactivation of MS2 viral particles in the presence of 5 mg L^–1 of SRNOM or 1 mg L^–1 of alginate. The EC-MWNT filter consistently maintained high performance over a wide range of solution pH and ionic strengths. The underlying mechanisms of enhanced viral removal and inactivation were further elucidated through EC-MWNT filtration experiments using carboxyl latex nanoparticles. We conclude that enhanced virus removal is attributed to the increased viral particle transport due to the applied external electric field and the attractive electrostatic interactions between the viral particles and the anodic MWNTs. The adsorbed viral particles on the MWNT surface are then inactivated through direct surface oxidation. Minimal fouling of the EC-MWNT filter was observed, even after 4-h filter runs with solutions containing 10 mg L^–1 of natural organic matter and 1 mM CaCl₂. Our results suggest that the EC-MWNT filter has a potential for use as a high performance point-of-use device for the removal of viruses from natural and contaminated waters with minimal power requirements