Highly-Efficient Sulfonated UiO-66(Zr) Optical Fiber for Rapid Detection of Trace Levels of Pb2.

Lead detection for biological environments, aqueous resources, and medicinal compounds, rely mainly on either utilizing bulky lab equipment such as ICP-OES or ready-made sensors, which are based on colorimetry with some limitations including selectivity and low interference. Remote, rapid and efficient detection of heavy metals in aqueous solutions at ppm and sub-ppm levels have faced significant challenges that requires novel compounds with such ability. Here, a UiO-66(Zr) metal-organic framework (MOF) functionalized with SO3H group (SO3H-UiO-66(Zr)) is deposited on the end-face of an optical fiber to detect lead cations (Pb2+) in water at 25.2, 43.5 and 64.0 ppm levels. The SO3H-UiO-66(Zr) system provides a Fabry-Perot sensor by which the lead ions are detected rapidly (milliseconds) at 25.2 ppm aqueous solution reflecting in the wavelength shifts in interference spectrum. The proposed removal mechanism is based on the adsorption of [Pb(OH2)6]2+ in water on SO3H-UiO-66(Zr) due to a strong affinity between functionalized MOF and lead. This is the first work that advances a multi-purpose optical fiber-coated functional MOF as an on-site remote chemical sensor for rapid detection of lead cations at extremely low concentrations in an aqueous system.

Proof of Concept for Light Conducting Membrane Substrate for UV-Activated Photocatalysis as an Alternative to Chemical Cleaning.

Adopting an effective strategy to control fouling is a necessary requirement for all membrane processes used in the water/wastewater treatment industry to operate sustainably. The use of ultraviolet (UV) activated photocatalysis has been shown to be effective in mitigating ceramic membrane fouling by natural organic matter. The widely used configuration in which light is directed through the polluted water to the membrane's active layer suffers from inefficiencies brought about by light absorption by the pollutants and light shielding by the cake layer. To address these limitations, directing light through the substrate, instead of through polluted water, was studied. A UV conducting membrane was prepared by dip coating TiO2 onto a sintered glass substrate. The substrate could successfully conduct UV from a lamp source, unlike a typical alumina substrate. The prepared membrane was applied in the filtration of a humic acid solution as a model compound to study natural organic matter membrane fouling. Directing UV through the substrate showed only a 1 percentage point decline in the effectiveness of the cleaning method over two cleaning events from 72% to 71%, while directing UV over the photocatalytic layer had a 9 percentage point decline from 84% to 75%. Adapting the UV-through-substrate configuration could be more useful in maintaining membrane functionality during humic acid filtration than the current method being used.

Dual Functional Ultrafiltration Membranes with Enzymatic Digestion and Thermo-Responsivity for Protein Self-Cleaning.

Controlling surface⁻protein interaction during wastewater treatment is the key motivation for developing functionally modified membranes. A new biocatalytic thermo-responsive poly vinylidene fluoride (PVDF)/nylon-6,6/poly(N-isopropylacrylamide)(PNIPAAm) ultrafiltration membrane was fabricated to achieve dual functionality of protein-digestion and thermo-responsive self-cleaning. The PVDF/nylon-6,6/PNIPAAm composite membranes were constructed by integrating a hydrophobic PVDF cast layer and hydrophilic nylon-6,6/PNIPAAm nanofiber layer on to which trypsin was covalently immobilized. The enzyme immobilization density on the membrane surface decreased with increasing PNIPAAm concentration, due to the decreased number of amine functional sites. An ultrafiltration study was performed using the synthetic model solution containing BSA/NaCl/CaCl2, where the PNIPAAm containing biocatalytic membranes demonstrated a combined effect of enzymatic and thermo-switchable self-cleaning. The membrane without PNIPAAm revealed superior fouling resistance and self-cleaning with an RPD of 22%, compared to membranes with 2 and 4 wt % PNIPAAm with 26% and 33% RPD, respectively, after an intermediate temperature cleaning at 50 °C, indicating that higher enzyme density offers more efficient self-cleaning than the combined effect of enzyme and PNIPAAm at low concentration. The conformational volume phase transition of PNIPAAm did not affect the stability of immobilized trypsin on membrane surfaces. Such novel surface engineering design offer a promising route to mitigate surface⁻protein contamination in wastewater applications.

Wetting phenomena in membrane distillation: Mechanisms, reversal, and prevention.

Membrane distillation (MD) is a rapidly emerging water treatment technology; however, membrane pore wetting is a primary barrier to widespread industrial use of MD. The primary causes of membrane wetting are exceedance of liquid entry pressure and membrane fouling. Developments in membrane design and the use of pretreatment have provided significant advancement toward wetting prevention in membrane distillation, but further progress is needed. In this study, a broad review is carried out on wetting incidence in membrane distillation processes. Based on this perspective, the study describes the wetting mechanisms, wetting causes, and wetting detection methods, as well as hydrophobicity measurements of MD membranes. This review discusses current understanding and areas for future investigation on the influence of operating conditions, MD configuration, and membrane non-wettability characteristics on wetting phenomena. Additionally, the review highlights mathematical wetting models and several approaches to wetting control, such as membrane fabrication and modification, as well as techniques for membrane restoration in MD. The literature shows that inorganic scaling and organic fouling are the main causes of membrane wetting. The regeneration of wetting MD membranes is found to be challenging and the obtained results are usually not favorable. Several pretreatment processes are found to inhibit membrane wetting by removing the wetting agents from the feed solution. Various advanced membrane designs are considered to bring membrane surface non-wettability to the states of superhydrophobicity and superomniphobicity; however, these methods commonly demand complex fabrication processes or high-specialized equipment. Recharging air in the feed to maintain protective air layers on the membrane surface has proven to be very effective to prevent wetting, but such techniques are immature and in need of significant research on design, optimization, and pilot-scale studies.

Charge tunable thin-film composite membranes by gamma-ray triggered surface polymerization.

Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100 nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1 v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45 mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70 L.m-2.h-1, whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.

Nanofiber Composite Membrane with Intrinsic Janus Surface for Reversed-Protein-Fouling Ultrafiltration.

Janus nanofiber based composite ultrafiltration (UF) membranes were fabricated via a two-step method, i.e., consecutive electrospinning of hydrophilic nylon-6,6/chitosan nanofiber blend and conventional casting of hydrophobic poly(vinylidene difluoride) (PVDF) dope solution. The as-developed PVDF/nylon-6,6/chitosan membranes were investigated for its morphology using Scanning Electron Microscopy (SEM) by which 18 wt % PVDF was chosen as the optimum base polymer concentration due to optimal degree of integration of cast and nanofiber layers. This membrane was benchmarked against the pure PVDF and PVDF/nylon-6,6 membranes in terms of surface properties, permeability, and its ability to reverse protein fouling. The improved hydrophilicity of the PVDF/nylon-6,6/chitosan membrane was revealed from the 72% reduction in the initial water contact angle compared to the pure PVDF benchmark, due to the incorporation of intrinsic hydrophilic hydroxyl and amine functional groups on the membrane surface confirmed by FTIR. The integration of the nanofiber and cast layers has led to altered pore arrangements offering about 93% rejection of bovine serum albumin (BSA) proteins with a permeance of 393 L·m-2·h-1·bar-1 in cross-flow filtration experiments; while the PVDF benchmark only had a BSA rejection of 67% and a permeance of 288 L·m-2·h-1·bar-1. The PVDF/nylon-6,6/chitosan membrane exhibited high fouling propensity with 2.2 times higher reversible fouling and 78% decrease in the irreversible fouling compared to the PVDF benchmark after 4 h of filtration with BSA foulants.

Towards Enhanced Performance Thin-film Composite Membranes via Surface Plasma Modification.

Advancing the design of thin-film composite membrane surfaces is one of the most promising pathways to deal with treating varying water qualities and increase their long-term stability and permeability. Although plasma technologies have been explored for surface modification of bulk micro and ultrafiltration membrane materials, the modification of thin film composite membranes is yet to be systematically investigated. Here, the performance of commercial thin-film composite desalination membranes has been significantly enhanced by rapid and facile, low pressure, argon plasma activation. Pressure driven water desalination tests showed that at low power density, flux was improved by 22% without compromising salt rejection. Various plasma durations and excitation powers have been systematically evaluated to assess the impact of plasma glow reactions on the physico-chemical properties of these materials associated with permeability. With increasing power density, plasma treatment enhanced the hydrophilicity of the surfaces, where water contact angles decreasing by 70% were strongly correlated with increased negative charge and smooth uniform surface morphology. These results highlight a versatile chemical modification technique for post-treatment of commercial membrane products that provides uniform morphology and chemically altered surface properties.

Mixed Matrix Carbon Molecular Sieve and Alumina (CMS-Al2O3) Membranes.

This work shows mixed matrix inorganic membranes prepared by the vacuum-assisted impregnation method, where phenolic resin precursors filled the pore of α-alumina substrates. Upon carbonisation, the phenolic resin decomposed into several fragments derived from the backbone of the resin matrix. The final stages of decomposition (>650 °C) led to a formation of carbon molecular sieve (CMS) structures, reaching the lowest average pore sizes of ~5 Å at carbonisation temperatures of 700 °C. The combination of vacuum-assisted impregnation and carbonisation led to the formation of mixed matrix of CMS and α-alumina particles (CMS-Al2O3) in a single membrane. These membranes were tested for pervaporative desalination and gave very high water fluxes of up to 25 kg m(-2) h(-1) for seawater (NaCl 3.5 wt%) at 75 °C. Salt rejection was also very high varying between 93-99% depending on temperature and feed salt concentration. Interestingly, the water fluxes remained almost constant and were not affected as feed salt concentration increased from 0.3, 1 and 3.5 wt%.

UiO-66 MOF end-face-coated optical fiber in aqueous contaminant detection.

Optical quality metal organic framework (MOF) thin films were integrated, for the first time, to the best of our knowledge, with structured optical fiber substrates to develop MOF-fiber sensors. The MOF-fiber structure, UiO-66 (Zr-based MOF is well known for its water stability), is a thin film that acts as an effective analyte collector. This provided a Fabry-Perot sensor in which concentrations of up to 15 mM Rhodamine-B were detected via wavelength shifts in the interference spectrum.

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion.

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

Properties of acid whey as a function of pH and temperature.

Compositional differences of acid whey (AW) in comparison with other whey types limit its processability and application of conventional membrane processing. Hence, the present study aimed to identify chemical and physical properties of AW solutions as a function of pH (3 to 10.5) at 4 different temperatures (15, 25, 40, or 90°C) to propose appropriate membrane-processing conditions for efficient use of AW streams. The concentration of minerals, mainly calcium and phosphate, and proteins in centrifuged supernatants was significantly lowered with increase in either pH or temperature. Lactic acid content decreased with pH decline and rose at higher temperatures. Calcium appeared to form complexes with phosphates and lactates mainly, which in turn may have induced molecular attractions with the proteins. An increase in pH led to more soluble protein aggregates with large particle sizes. Surface hydrophobicity of these particles increased significantly with temperature up to 40°C and decreased with further heating to 90°C. Surface charge was clearly pH dependent. High lactic acid concentrations appeared to hinder protein aggregation by hydrophobic interactions and may also indirectly influence protein denaturation. Processing conditions such as pH and temperature need to be optimized to manipulate composition, state, and surface characteristics of components of AW systems to achieve an efficient separation and concentration of lactic acid and lactose.

Changes in glucose fermentation pathways by an enriched bacterial culture in response to regulated dissolved H2 concentrations.

It is well established that metabolic pathways in the fermentation of organic waste are primarily controlled by dissolved H2 concentrations, but there is no reported study that compares observed and predicted shifts in fermentation pathways induced by manipulating the dissolved H2 concentration. A perfusion system is presented that was developed to control dissolved H2 concentrations in the continuous fermentation of glucose by a culture highly enriched towards Thermoanaerobacterium thermosaccharolyticum (86 ± 9% relative abundance) from an originally diverse consortia in the leachate of a laboratory digester fed with municipal solid waste. Media from a 2.5 L CSTR was drawn through sintered steel membrane filters to retain biomass, allowing vigorous sparging in a separate chamber without cellular disruption. Through a combination of sparging and variations in glucose feeding rate from 0.8 to 0.2 g/L/d, a range of steady state fermentations were performed with dissolved H2 concentrations as low as an equivalent equilibrated H2 partial pressure of 3 kPa. Trends in product formation rates were simulated using a H2 regulation partitioning model. The model correctly predicted the direction of products redistribution in response to H2 concentration changes and the acetate and butyrate formation rates when H2 concentrations were less than 6 kPa. However, the model over-estimated acetate, ethanol and butanol productions at the expense of butyrate production at higher H2 concentrations. The H2 yield at the lowest dissolved H2 concentration was 2.67 ± 0.08 mol H2 /mol glucose, over 300% higher than the yield achieved in a CSTR operated without sparging.