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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.

Electrically conducting membranes (ECMs) have been reported to be efficient in fouling prevention and destruction of aqueous chemical compounds. In the current study, highly conductive and anodically stable composite polyaniline-carbon nanotube (PANI-CNT) ultrafiltration (UF) ECMs were fabricated through a process of electropolymerization of aniline on a CNT substrate under acidic conditions. The resulting PANI-CNT UF ECMs were characterized by scanning electron microscopy, atomic force microscopy, a four-point conductivity probe, cyclic voltammetry, and contact angle goniometry. The utilization of the PANI-CNT material led to significant advantages, including: (1) increased electrical conductivity by nearly an order of magnitude; (2) increased surface hydrophilicity while not impacting membrane selectivity or permeability; and (3) greatly improved stability under anodic conditions. The membrane's anodic stability was evaluated in a pH-controlled aqueous environment under a wide range of anodic potentials using a three-electrode cell. Results indicate a significantly reduced degradation rate in comparison to a CNT-poly(vinyl alcohol) ECM under high anodic potentials. Fouling experiments conducted with bovine serum albumin demonstrated the capacity of the PANI-CNT ECMs for in situ oxidative cleaning, with membrane flux restored to its initial value under an applied potential of 3 V. Additionally, a model organic compound (methylene blue) was electrochemically transformed at high efficiency (90%) in a single pass through the anodically charged ECM.

Hexavalent chromium (Cr(VI)) contamination in drinking water resources remains a challenge in many parts of the United States, as well as in regions affected by industrial pollution. In this study, we demonstrated how electrically conducting carbon nanotube (CNT)polyvinyl alcohol (PVA) composite ultrafiltration (UF) membranes can be used to remove Cr(VI) from water through a combined process of electrostatic repulsion, electrochemical reduction, and precipitation. The impact of different operational (flux, contact time, applied electrical potential) and environmental (pH and salinity) conditions on Cr(VI) removal were evaluated. Due to the native electrical potential of the CNT/PVA UF membrane material, approximately 45% removal of 1 ppm Cr(VI) solution was detected under neutral pH conditions in deionized water. Increased Cr(VI) removal was observed with increasing membrane surface charge density, which was accomplished through the application of an external potential (3V, 5V and 7V, membrane as cathode) to the electrically conductive membrane surface. The solution ionic strength showed a significant impact on Cr(VI) removal. By increasing the ionic strength without applying external potential on the membrane, the electrostatic repulsive force between the charged membrane surface and the CrO 4 2ion was eliminated, and Cr(VI) removal dropped to zero. The highest removal (95%) was achieved when 7V was applied to the membrane/counter electrode with a 6 µm-thick membrane. Here, Cr(VI) was electrochemically reduced to Cr(III) on the membrane surface, followed by Cr(III) precipitation as chromium hydroxide Cr(OH) 3(s) , which occurred by Cr(III) reacting with hydroxide ions generated via water splitting on the CNT network. Precipitated Cr(OH) 3 was then removed by the UF membrane. In addition, CNT-PVA UF membranes were used to treat tap water spiked with Cr(VI); under these conditions, 99% Cr(VI) removal was observed when 7V were applied to the membrane/counter electrode. Furthermore, we demonstrate that other trace inorganic contaminants, such as uranium, were effectively removed as well.

Oil/water separations have become an area of great interest, as growing oil extraction activities are increasing the generation of oily wastewaters as well as increasing the risk of oil spills. Here, we demonstrate a membrane-based and fouling-free oil/water separation method that couples carbon nanotube-poly(vinyl alcohol) underwater superoleophobic ultrafiltration membranes with magnetic Pickering emulsions. We demonstrate that this process is insensitive to low water temperatures, high ionic strength, or crude oil loading, while allowing operation at high permeate fluxes and producing high quality permeate. Furthermore, we develop a theoretical framework that analyzes the stability of Pickering emulsions under filtration mechanics, relating membrane surface properties and hydrodynamic conditions in the Pickering emulsion cake layer to membrane performance. Finally, we demonstrate the recovery and recyclability of the nanomagnetite used to form the Pickering emulsions through a magnetic separation step, resulting in an environmentally friendly, continuous process for oil/water separation.

The electrochemical prevention and removal of CaSO4 and CaCO3 mineral scales on electrically conducting carbon nanotube - polyamide reverse osmosis membrane was investigated. Different electrical potentials were applied to the membrane surface while filtering model scaling solutions with high saturation indices. Scaling progression was monitored through flux measurements. CaCO3 scale was efficiently removed from the membrane surface through the intermittent application of a 2.5 V potential to the membrane surface, when the membrane acted as an anode. Water oxidation at the anode, which led to proton formation, resulted in the dissolution of deposited CaCO3 crystals. CaSO4 scale formation was significantly retarded through the continuous application of 1.5 V DC to the membrane surface, when the membrane was operated as an anode. The continuous application of a sufficient electrical potential to the membrane surface leads to the formation of a thick layer of counter-ions along the membrane surface that pushed CaSO4 crystal formation away from the membrane surface, allowing the formed crystals to be carried away by the cross-flow. We developed a simple model, based on a modified Poisson-Boltzmann equation, which qualitatively explained our observed experimental results.

The desalination of inland brackish groundwater offers the opportunity to provide potable drinking water to residents and industrial cooling water to industries located in arid regions. Geothermal brines are used to generate electricity, but often contain high concentrations of dissolved salt. Here, we demonstrate how the residual heat left in spent geothermal brines can be used to drive a membrane distillation (MD) process and recover desalinated water. Porous polypropylene membranes were coated with a carbon nanotube (CNT)/poly(vinyl alcohol) layer, resulting in composite membranes having a binary structure that combines the hydrophobic properties critical for MD with the hydrophilic and conductive properties of the CNTs. We demonstrate that the addition of the CNT layer increases membrane flux due to enhanced heat transport from the bulk feed to the membrane surface, a result of CNT's high thermal transport properties. Furthermore, we show how hydroxide ion generation, driven by water electrolysis on the electrically conducting membrane surface, can be used to efficiently dissolve silicate scaling that developed during the process of desalinating the geothermal brine, negating the need for chemical cleaning.

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