Developing technologies for the reduction of biofouling and enhancement of membrane functionality and durability are challenging but critical for the advancement of water purification processes. Silver (Ag) is often used in the process of purification due to its anti-fouling properties; however, the leaching of this metal from a filtration membrane significantly reduces its effectiveness. Our study was designed to integrate the positive characteristics of poly vinyl alcohol (PVA) with the controlled incorporation of nano-scale silver ions across the membrane. This approach was designed with three goals in mind: (1) to improve antifouling activity; (2) to prevent leaching of the metal; and (3) to extend the durability of the functionalized membrane. The fabrication method we used was a modified version of manual coating in combination with sufficient pressure to ensure impregnation and proper blending of PVA with cellulose acetate. We then used the spin coater to enhance the cross-linking reaction, which improved membrane durability. Our results indicate that PVA acts as a reducing agent of Ag+ to Ag0 using X-ray photoelectron spectroscopy analysis and demonstrate that the metal retention was increased by more than 90% using PVA in combination with ultraviolet-photo-irradiated Ag+ reduced to Ag0. The Ag+ ions have sp hybrid orbitals, which accept lone pairs of electrons from a hydroxyl oxygen atom, and the covalent binding of silver to the hydroxyl groups of PVA enhanced retention. In fact, membranes with reduced Ag displayed a more effective attachment of Ag and a more efficient eradication of E. coli growth. Compared to pristine membranes, bovine serum albumin (BSA) flux increased by 8% after the initial addition of Ag and by 17% following ultraviolet irradiation and reduction of Ag, whereas BSA rejection increased by 10% and 11%, respectively. The implementation of this hybrid method for modifying commercial membranes could lead to significant savings due to increased metal retention and membrane effectiveness. These enhancements would ultimately increase the membrane’s longevity and reduce the cost/benefit ratio.
Microcystin-LR (MC-LR) is a toxin produced by cyanobacteria that can bloom in freshwater supplies. This study describes a new strategy for remediation of MC-LR that combines linearization of the toxin using microcystinase A, MlrA, enzyme with rejection of linearized byproducts using membrane filtration. The MlrA enzyme was expressed in Escherichia coli (E. coli) and purified via a His-tag with 95% purity. Additionally, composite membranes made of 95% polysulfone and 5% sulfonated polyether ether ketone (SPEEK) were fabricated and used to filter a solution containing cyclic and linearized MC-LR. Tests were also performed to measure the adsorption and desorption of MC-LR on polysulfone/SPEEK membranes. Liquid chromatography-mass spectrometry (LC-MS) was used to characterize the progress of linearization and removal of MC-LR. Results indicate that the MlrA was successful at linearizing MC-LR. Membrane filtration tests showed rejection of 97% of cyclic MC-LR and virtually all linearized MC-LR, with adsorption to the membranes being the main rejection mechanism. Adsorption/desorption tests indicated that methanol could be used to strip residual MC-LR from membranes to regenerate them. This study demonstrates a novel strategy of remediation of microcystin-tainted water, combining linearization of MC-LR to a low-toxicity byproduct along with removal by membrane filtration.
Polymeric membrane fouling is a long-standing challenge for water filtration. Metal/metal oxide nanoparticle functionalization of the membrane surface can impart anti-fouling properties through the reactivity of the metal species and the generation of radical species. Copper oxide nanoparticles (CuO NPs) are effective at reducing organic fouling when used in conjunction with hydrogen peroxide, but leaching of copper ions from the membrane has been observed, which can hinder the longevity of the CuO NP activity at the membrane surface. Zwitterions can reduce organic fouling and stabilize NP attachment, suggesting a potential opportunity to combine the two functionalizations. Here, we coated polyethersulfone (PES) ultrafiltration membranes with polydopamine (PDA) and attached the zwitterionic compound, thiolated 2-methacryloyloxyethyl phosphorylcholine (MPC-SH), and CuO NPs. Functionalized membranes resulted in a higher flux recovery ratio (0.694) than the unfunctionalized PES control (0.599). Copper retention was high (>96%) for functionalized membranes. The results indicate that CuO NPs and MPC-SH can reduce organic fouling with only limited copper leaching.
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