In situ formation of silver nanoparticles on thin-film composite reverse osmosis membranes for biofouling mitigation.

The potential to incorporate silver nanoparticles (Ag-NPs) as biocides in membranes for water purification has gained much interest in recent years. However, a viable strategy for loading the Ag-NPs on the membrane remains challenging. This paper presents a novel, facile procedure for loading Ag-NPs on thin-film composite (TFC) reverse osmosis membranes. Reaction of silver salt with a reducing agent on the membrane surface resulted in uniform coverage of Ag-NPs, irreversibly bound to the membrane, as confirmed by XPS, TEM, and SEM analyses. Salt selectivity of the membrane as well its surface roughness, hydrophilicity, and zeta potential were not impacted by Ag-NP functionalization, while a slight reduction (up to 17%) in water permeability was observed. The formed Ag-NPs imparted strong antibacterial activity to the membrane, leading to reduction of more than 75% in the number of live bacteria attached to the membrane for three model bacteria strains. In addition, confocal microscopy analyses revealed that Ag-NPs significantly suppressed biofilm formation, with 41% reduction in total biovolume and significant reduction in EPS, dead, and live bacteria on the functionalized membrane. The simplicity of the method, the short reaction time, the ability to load the Ag-NPs on site, and the strong imparted antibacterial activity highlight the potential of this method in real-world RO membrane applications.

Surface functionalization of thin-film composite membranes with copper nanoparticles for antimicrobial surface properties.

Biofouling is a major operational challenge in reverse osmosis (RO) desalination, motivating a search for improved biofouling control strategies. Copper, long known for its antibacterial activity and relatively low cost, is an attractive potential biocidal agent. In this paper, we present a method for loading copper nanoparticles (Cu-NPs) on the surface of a thin-film composite (TFC) polyamide RO membrane. Cu-NPs were synthesized using polyethyleneimine (PEI) as a capping agent, resulting in particles with an average radius of 34 nm and a copper content between 39 and 49 wt.%. The positive charge of the Cu-NPs imparted by the PEI allowed a simple electrostatic functionalization of the negatively charged RO membrane. We confirmed functionalization and irreversible binding of the Cu-NPs to the membrane surface with SEM and XPS after exposing the membrane to bath sonication. We also demonstrated that Cu-NP functionalization can be repeated after the Cu-NPs dissolve from the membrane surface. The Cu-NP functionalization had minimal impact on the intrinsic membrane transport parameters. Surface hydrophilicity and surface roughness were also maintained, and the membrane surface charge became positive after functionalization. The functionalized membrane exhibited significant antibacterial activity, leading to an 80-95% reduction in the number of attached live bacteria for three different model bacterial strains. Challenges associated with this functionalization method and its implementation in RO desalination are discussed.

Control of biofouling on reverse osmosis polyamide membranes modified with biocidal nanoparticles and antifouling polymer brushes.

Thin-film composite (TFC) polyamide reverse osmosis (RO) membranes are prone to biofouling due to their inherent physicochemical surface properties. In order to address the biofouling problem, we have developed novel surface coatings functionalized with biocidal silver nanoparticles (AgNPs) and antifouling polymer brushes via polyelectrolyte layer-by-layer (LBL) self-assembly. The novel surface coating was prepared with polyelectrolyte LBL films containing poly(acrylic acid) (PAA) and poly(ethylene imine) (PEI), with the latter being either pure PEI or silver nanoparticles coated with PEI (Ag-PEI). The coatings were further functionalized by grafting of polymer brushes, using either hydrophilic poly(sulfobetaine) or low surface energy poly(dimethylsiloxane) (PDMS). The presence of both LBL films and sulfobetaine polymer brushes at the interface significantly increased the hydrophilicity of the membrane surface, while PDMS brushes lowered the membrane surface energy. Overall, all surface modifications resulted in significant reduction of irreversible bacterial cell adhesion. In microbial adhesion tests with E. coli bacteria, a normalized cell adhesion in the range of only 4 to 16% on the modified membrane surfaces was observed. Modified surfaces containing silver nanoparticles also exhibited strong antimicrobial activity. Membranes coated with LBL films of PAA/Ag-PEI achieved over 95% inactivation of bacteria attached to the surface within 1 hour of contact time. Both the antifouling and antimicrobial results suggest the potential of using these novel surface coatings in controlling the fouling of RO membranes.

Desalination and reuse of high-salinity shale gas produced water: drivers, technologies, and future directions.

In the rapidly developing shale gas industry, managing produced water is a major challenge for maintaining the profitability of shale gas extraction while protecting public health and the environment. We review the current state of practice for produced water management across the United States and discuss the interrelated regulatory, infrastructure, and economic drivers for produced water reuse. Within this framework, we examine the Marcellus shale play, a region in the eastern United States where produced water is currently reused without desalination. In the Marcellus region, and in other shale plays worldwide with similar constraints, contraction of current reuse opportunities within the shale gas industry and growing restrictions on produced water disposal will provide strong incentives for produced water desalination for reuse outside the industry. The most challenging scenarios for the selection of desalination for reuse over other management strategies will be those involving high-salinity produced water, which must be desalinated with thermal separation processes. We explore desalination technologies for treatment of high-salinity shale gas produced water, and we critically review mechanical vapor compression (MVC), membrane distillation (MD), and forward osmosis (FO) as the technologies best suited for desalination of high-salinity produced water for reuse outside the shale gas industry. The advantages and challenges of applying MVC, MD, and FO technologies to produced water desalination are discussed, and directions for future research and development are identified. We find that desalination for reuse of produced water is technically feasible and can be economically relevant. However, because produced water management is primarily an economic decision, expanding desalination for reuse is dependent on process and material improvements to reduce capital and operating costs.

Fouling mitigation by iron-based electroflocculation in microfiltration: Mechanisms and energy minimization.

High-energy demand presents a major obstacle in the application of advanced water-purification systems. In this work, energy minimization and fouling mitigation by iron-based electroflocculation in dead-end microfiltration were investigated. Highly pure water contaminated with Silica-CMP (chemical mechanical polishing) particles were pretreated by electroflocculation at short operation times and a constant electrical current intensity of 0.4 A, followed by different slow-mixing times and filtration without any sedimentation step. By using a new method for filtration-energy appraisal, we found that an over 90% reduction in filtration energy could be achieved. The improvement was observed at all pH values examined (pH 6-8); pH values below 7 were problematic because the permeate turned yellow as a result of residual iron. The appearance of residual iron was explained by the dependence of Fe(2+) to Fe(3+) reaction rates on pH. Scanning electron micrographs of the fouled membrane surface showed the important role played by the sweep-coagulation mechanism in mitigating fouling. When internal fouling was the dominant mechanism, the amorphous iron-hydroxide solids formed a layer that filtered out the primary particles, protecting the membrane pores from plugging. Iron-hydroxide particles also reduced the hydraulic resistance of the cake when the external fouling mechanism dominated. Significant energy reduction was observed, even without the slow-mixing step, as a result of the local flocculation conditions near the membrane surface. Additional energy savings were obtained due to the significantly higher initial-flux restoration rates (>90%) resulting from electroflocculation pretreatment.

Iron-oxidation processes in an electroflocculation (electrocoagulation) cell.

The processes of iron oxidation in an electroflocculation cell were investigated for a pH range of 5-9 and electric currents of 0.05-0.4A (equivalent current densities of 8.6-69 A/m(2)). At all pH values and electric currents investigated, it was demonstrated and proven that for all practical purposes, the form of iron that dissolves from the anode is Fe(2+) (ferrous). The difference between the amount of theoretical dissolution as calculated by Faraday's law and the amount of observed dissolved iron ions may indicate two phenomena in electrochemical cells. The first is possible dissolution of the anode even without the operation of an electric current; this led to higher theoretical dissolution rates at lower pH. The second is the participation of some of the electrons of the electric current in reactions other than anode dissolution which led to lower theoretical dissolution rates at higher pH. Those other reactions did not lead to an increase in the local oxidation saturation level near the anode and did not affect iron-oxidation rates in the electroflocculation processes. The oxidation rates of the dissolved Fe(2+) (ferrous) to Fe(3+) (ferric) ions in electroflocculation processes were strongly dependent on the pH and were similar to the known oxidation rates of iron in non-electrochemical cells.