Machine Learning for Polymer Design to Enhance Pervaporation-Based Organic Recovery.

Pervaporation (PV) is an effective membrane separation process for organic dehydration, recovery, and upgrading. However, it is crucial to improve membrane materials beyond the current permeability-selectivity trade-off. In this research, we introduce machine learning (ML) models to identify high-potential polymers, greatly improving the efficiency and reducing cost compared to conventional trial-and-error approach. We utilized the largest PV data set to date and incorporated polymer fingerprints and features, including membrane structure, operating conditions, and solute properties. Dimensionality reduction, missing data treatment, seed randomness, and data leakage management were employed to ensure model robustness. The optimized LightGBM models achieved RMSE of 0.447 and 0.360 for separation factor and total flux, respectively (logarithmic scale). Screening approximately 1 million hypothetical polymers with ML models resulted in identifying polymers with a predicted permeation separation index >30 and synthetic accessibility score <3.7 for acetic acid extraction. This study demonstrates the promise of ML to accelerate tailored membrane designs.

Multistage Surface-Heated Vacuum Membrane Distillation Process Enables High Water Recovery and Excellent Heat Utilization: A Modeling Study.

Surface-heated membrane distillation (MD) enhances the energy efficiency of desalination by mitigating temperature polarization (TP). However, systematic investigations of larger scale, multistage, surface-heated MD system with high water recovery and heat recycling are limited. Here, we explore the design and performance of a multistage surface-heated vacuum MD (SHVMD) with heat recovery through a comprehensive finite difference model. In this process, the latent heat of condensation is recovered through an internal heat exchanger (HX) using the retentate from one stage as the condensing fluid for the next stage and an external HX using the feed as the condensing fluid. Model results show that surface heating enhances the performance compared to conventional vacuum MD (VMD). Specifically, in a six-stage SHVMD process, 54.44% water recovery and a gained output ratio (GOR) of 3.28 are achieved with a surface heat density of 2000 W m-2, whereas a similar six-stage VMD process only reaches 18.19% water recovery and a GOR of 2.15. Mass and energy balances suggest that by mitigating TP, surface heating increases the latent heat trapped in vapor. The internal and external HXs capture and reuse the additional heat, which enhances the GOR values. We show for SHVMD that the hybrid internal/external heat recovery design can have GOR value 1.44 times higher than that of systems with only internal or external heat recovery. Furthermore, by only increasing six stages to eight stages, a GOR value as high as 4.35 is achieved. The results further show that surface heating can reduce the energy consumption of MD for brine concentration. The multistage SHVMD technology exhibits a promising potential for the management of brine from industrial plants.

Mineral Scale Prevention on Electrically Conducting Membrane Distillation Membranes Using Induced Electrophoretic Mixing.

The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.

Scalable antifouling reverse osmosis membranes utilizing perfluorophenyl azide photochemistry.

We present a method to produce anti-fouling reverse osmosis (RO) membranes that maintains the process and scalability of current RO membrane manufacturing. Utilizing perfluorophenyl azide (PFPA) photochemistry, commercial reverse osmosis membranes were dipped into an aqueous solution containing PFPA-terminated poly(ethyleneglycol) species and then exposed to ultraviolet light under ambient conditions, a process that can easily be adapted to a roll-to-roll process. Successful covalent modification of commercial reverse osmosis membranes was confirmed with attenuated total reflectance infrared spectroscopy and contact angle measurements. By employing X-ray photoelectron spectroscopy, it was determined that PFPAs undergo UV-generated nitrene addition and bind to the membrane through an aziridine linkage. After modification with the PFPA-PEG derivatives, the reverse osmosis membranes exhibit high fouling-resistance.

Bacteria-polymeric membrane interactions: atomic force microscopy and XDLVO predictions.

Atomic force microscopy (AFM) in conjunction with a bioprobe developed using a polydopamine wet adhesive was used to directly measure the adhesive force between bacteria and different polymeric membrane surfaces. Bacterial cells of Pseudomonas putida and Bacillus subtilis were immobilized onto the tip of a standard AFM cantilever, and force measurements made using the modified cantilever on various membranes. Interaction forces measured with the bacterial probe were compared, qualitatively, to predictions by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory with steric interactions included. The XDLVO theory predicted attractive interactions between low energy hydrophobic membranes with high energy hydrophilic bacterium (P. putida). It also predicted a shallow primary maximum with the most hydrophilic bacterium, B. subtilis . Discrepancies between predictions using the XDLVO theory and theory require involvement of factors such as bridging effects. Differences in interaction between P. putida and B. subtilis are attributed to acid-base interactions and steric interactions. P. putida is Gram negative with lipopolysaccharides present in the outer cell membrane. A variation in forces of adhesion for bacteria on polymeric membranes studied was interpreted in terms of hydrophilicity and interfacial surface potential calculated from physicochemical properties.

Biological treatment of perfluorooctanesulfonic acid (PFOS) using microbial capsules of a polysulfone membrane.

Perfluorooctanesulfonic acid (PFOS) is a persistent organic substance that has been extensively applied in many industries and causes severe, widespread adverse health impacts on humans and the environment. The development of an effective PFOS treatment method with affordable operational costs has been expected. This study proposes the biological treatment of PFOS using microbial capsules enclosing a PFOS-reducing microbial consortium. The objective of this study was to evaluate the performance of the polymeric membrane encapsulation technique for the biological removal of PFOS. First, a PFOS-reducing bacterial consortium, composed of Paracoccus (72%), Hyphomicrobium (24%), and Micromonosporaceae (4%), was enriched from activated sludge by acclimation and subsequent subculturing with PFOS containing media. The bacterial consortium was first immobilized in alginate gel beads, then enclosed in membrane capsules by coating the gel beads with a 5% or 10% polysulfone (PSf) membrane. The introduction of microbial membrane capsules could increase PFOS reduction to between 52% and 74% compared with free cell suspension, which reduced by 14% over three weeks. Microbial capsules coated with 10% PSf membrane demonstrated the highest PFOS reduction at 80% and physical stability for six weeks. Candidate metabolites including perfluorobutanoic acid (PFBA) and 3,3,3- trifluoropropionic acid were detected by FTMS, suggesting the possible biological degradation of PFOS. In microbial membrane capsules, the initial adsorption of PFOS on the shell membrane layer enhanced subsequent biosorption and biological degradation by PFOS-reducing bacteria immobilized in the core alginate gel beads. The 10%-PSf microbial capsules exhibited a thicker membrane layer with the fabric structure of a polymer network, which maintained longer physical stability than 5%-PSf microbial capsules. This outcome suggests the potential application of microbial membrane capsules to PFOS-contaminated water treatment.

Tuning structure and properties of graded triblock terpolymer-based mesoporous and hybrid films.

Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 10(14) per m(2) above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery.

Desalinating a real hyper-saline pre-treated produced water via direct-heat vacuum membrane distillation.

Membrane distillation (MD) is an emerging thermal desalination technology capable of desalinating waters of any salinity. During typical MD processes, the saline feedwater is heated and acts as the thermal energy carrier; however, temperature polarization (as well as thermal energy loss) contributes to low distillate fluxes, low single-pass water recovery and poor thermal efficiency. An alternative approach is to integrate an extra thermal energy carrier as part of the membrane and/or module assembly, which can channel externally provided heat directly to the membrane-feedwater interface and/or along the feed channel length. This direct-heat delivery has been demonstrated to increase single-pass water recovery and enhance the overall thermal efficiency. We developed a bench-scale direct-heated vacuum MD (DHVMD) process to desalinate pre-treated oil and gas "produced water" with an initial total dissolved solids of 115,500 ppm at a feed temperature ranging between 24 and 32 °C. We evaluated both water flux and specific energy consumption (SEC) as a function of water recovery. The system achieved a 50% water recovery without significant scaling, with an average flux >6 kg m-2 hr-1 and a SEC as low as 2,530 kJ kg-1. The major species of mineral scales (i.e., NaCl, CaSO4, and SrSO4) that limited the water recovery to 68% were modeled in terms of thermodynamics and identified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. In addition, we further developed and employed a physics-based process model to estimate temperature, salinity, water transport and energy flows for full-scale vacuum MD and DHVMD modules. Model results show that a direct-heat input rate of 3,600 W can increase single-pass water recovery from 2.1% to 3.1% while lowering the thermal SEC from 7,800 kJ kg-1 to 6,517 kJ kg-1 in an unoptimized module. Finally, the scaling up potential of DHVMD process is briefly discussed.

Distribution of microplastics in soil and freshwater environments: Global analysis and framework for transport modeling.

Microplastics are continuously released into the terrestrial environment from sources where they are used and produced. These microplastics accumulate in soils, sediments, and freshwater bodies, and some are conveyed via wind and water to the oceans. The concentration gradient between terrestrial inland and coastal regions, the factors that influence the concentration, and the fundamental transport processes that could dynamically affect the distribution of microplastics are unclear. We analyzed microplastic concentration reported in 196 studies from 49 countries or territories from all continents and found that microplastic concentrations in soils or sediments and surface water could vary by up to eight orders of magnitude. Mean microplastic concentrations in inland locations such as glacier (191 n L-1) and urban stormwater (55 n L-1) were up to two orders of magnitude greater than the concentrations in rivers (0.63 n L-1) that convey microplastics from inland locations to water bodies in terrestrial boundary such as estuaries (0.15 n L-1). However, only 20% of studies reported microplastics below 20 µm, indicating the concentration in these systems can change with the improvement of microplastic detection technology. Analysis of data from laboratory studies reveals that biodegradation can also reduce the concentration and size of deposited microplastics in the terrestrial environment. Fiber percentage was higher in the sediments in the coastal areas than the sediments in inland water bodies, indicating fibers are preferentially transported to the terrestrial boundary. Finally, we provide theoretical frameworks to predict microplastics transport and identify potential hotspots where microplastics may accumulate.

Understanding biophysicochemical interactions at the nano-bio interface.

Rapid growth in nanotechnology is increasing the likelihood of engineered nanomaterials coming into contact with humans and the environment. Nanoparticles interacting with proteins, membranes, cells, DNA and organelles establish a series of nanoparticle/biological interfaces that depend on colloidal forces as well as dynamic biophysicochemical interactions. These interactions lead to the formation of protein coronas, particle wrapping, intracellular uptake and biocatalytic processes that could have biocompatible or bioadverse outcomes. For their part, the biomolecules may induce phase transformations, free energy releases, restructuring and dissolution at the nanomaterial surface. Probing these various interfaces allows the development of predictive relationships between structure and activity that are determined by nanomaterial properties such as size, shape, surface chemistry, roughness and surface coatings. This knowledge is important from the perspective of safe use of nanomaterials.

Tailoring the structure of thin film nanocomposite membranes to achieve seawater RO membrane performance.

Herein we report on the formation and characterization of pure polyamide thin film composite (TFC) and zeolite-polyamide thin film nanocomposite (TFN) reverse osmosis (RO) membranes. Four different physical-chemical post-treatment combinations were applied after the interfacial polymerization reaction to change the molecular structure of polyamide and zeolite-polyamide thin films. Both TFC and TFN hand-cast membranes were more permeable, hydrophilic, and rough than a commercial seawater RO membrane. Salt rejection by TFN membranes was consistently below that of hand-cast TFC membranes; however, two TFN membranes exhibited 32 g/L NaCl rejections above 99.4%, which was better than the commercial membrane under the test conditions employed. The nearly defect-free TFN films that produced such high rejections were achieved only with wet curing, regardless of other post-treatments. Polyamide films formed in the presence of zeolite nanoparticles were less cross-linked than similarly cast pure polyamide films. At the very low nanoparticle loadings evaluated, differences between pure polyamide and zeolite-polyamide membrane water and salt permeability correlated weakly with extent of cross-linking of the polyamide film, which suggests that defects and molecular-sieving largely govern transport through zeolite-polyamide thin film nanocomposite membranes.

Low-Fouling Antibacterial Reverse Osmosis Membranes via Surface Grafting of Graphene Oxide.

Azide-functionalized graphene oxide (AGO) was covalently anchored onto commercial reverse osmosis (RO) membrane surfaces via azide photochemistry. Surface modification was carried out by coating the RO membrane with an aqueous dispersion of AGO followed by UV exposure under ambient conditions. This simple process produces a hydrophilic, smooth, antibacterial membrane with limited reduction in water permeability or salt selectivity. The GO-RO membrane exhibited a 17-fold reduction in biofouling after 24 h of Escherichia coli contact and almost 2 times reduced BSA fouling after a 1 week cross-flow test compared to its unmodified counterpart.

Effects of membrane orientation on fouling characteristics of forward osmosis membrane in concentration of microalgae culture.

Application of forward osmosis (FO) membrane to microalgae cultivation processes enables concentration of microalgae and nutrients with low energy consumption. To understand fouling characteristics of FO membrane in concentration of microalgae culture, we studied flux decline, flux recovery by cleaning, and foulants characteristics, in different membrane orientation of active-layer-facing-feed-solution (AL-FS) and active-layer-facing-draw-solution (AL-DS) modes. Batch concentration of Chlorella vulgaris was conducted with a cellulose-triacetate FO membrane. Rapid flux decline and lower flux recovery was observed in AL-DS mode because of inner-membrane fouling including internal pore clogging, adsorption and internal concentration polarization in the support layer. A proportion of polysaccharides in extracellular polymeric substances to soluble microbial products were larger in chemical cleaning effluent than physical one in AL-DS mode, although those were not significantly different in AL-FS mode. Excitation-emission matrix analysis revealed that proteins and humic-like substances were also possible irreversible foulants both in AL-DS and AL-FS modes.

Removing cadmium ions from water via nanoparticle-enhanced ultrafiltration.

Here we evaluate removal of cadmium ions from water by nanoparticle-enhanced ultrafiltration using polymer and zeolite nanoparticles. This evaluation considered nanoparticle physical-chemical properties, metal-binding kinetics, capacity and reversibility, and ultrafiltration separation for a Linde type A zeolite nanocrystals, poly(acrylic acid), alginic acid, and carboxyl-functionalized PAMAM dendrimers in simple, laboratory prepared ionic solutions. The three synthetic materials exhibited fast binding kinetics and strong affinity for cadmium, with good regeneration capabilities. Only the zeolite nanoparticles were completely rejected by the ultrafiltration membranes tested. Overall, colloidal zeolites performed similar to conventional metal binding polymers, but were more easily recovered using relatively loose filtration membranes (i.e., lower energy consumption). Further, the superhydrophilic colloidal zeolites caused relatively little flux decline even in the presence of divalent cations which caused dense, highly impermeable polymer gels to form over the membranes. These results suggest zeolite nanoparticles may compete with polymeric materials in low-pressure hybrid filtration processes designed to remove toxic metals from water.

High-content screening for biofilm assays.

The authors describe a novel high-throughput screening platform that provides rapid, reliable, quantitative assessment of biofilm formation and removal on engineered surfaces. Unlike traditional biofilm assays based on plate readers, this assay platform is based on high-content screening, which allows for multiplexing to simultaneously quantify the number of bacterial adhesions per unit area and the viability of adhered cells using fluorescent dye combinations. This platform is fully automated and has a throughput of more than 10,000 wells per day. The authors used this platform to examine the influence of different assay buffer systems on bacterial adhesion, viability, and removal on cross-linked polyvinyl alcohol coating films synthesized directly onto the bottoms of 384-well plates. The results indicated that water chemistry, bacteria cell type, and film chemistry combine to govern biofilm formation. In general, both reversible and irreversible bacterial adhesion increased with the extent of cross-linking in coating films, which correlates strongly with coating film cross-linking degree and hydrophobicity, which is closely related. The high-throughput platform offers a powerful tool for rapid evaluation of fouling-resistant coating films in addition to elucidation of fundamental mechanisms governing bacterial adhesion.

Direct observation of bacterial deposition onto clean and organic-fouled polyamide membranes.

Nanofiltration (NF) and reverse osmosis (RO) membranes are commonly applied to produce highly purified water from municipal wastewater effluents. In these applications, biofouling limits overall process performance and increases the cost of operation. Initial bacteria adhesion onto a membrane surface is a critical early step in the overall process of membrane biofouling. However, adsorption of effluent organic matter onto the membrane may precede bacterial deposition and change membrane surface properties. Herein we employed direct microscopic observation to elucidate mechanisms governing bacterial cell deposition onto clean and organic-fouled NF and RO membranes. Bovine serum albumin (BSA) and alginic acid (AA) were used as models for protein and polysaccharide rich organic matter in secondary wastewater effluents. In all experiments, organic fouling increased membrane hydraulic resistance and salt rejection, in addition to interfacial hydrophilicity and roughness. Even though surface hydrophilicity increased, the rougher surfaces presented by organic-fouled membranes produced nano-scale features that promoted localized bacterial deposition. An extended DLVO analysis of bacterial cells and membrane surface properties suggested that bacterial deposition correlated most strongly with the Lewis acid-base free energy of adhesion and root mean square (RMS) roughness, whereas van der Waals and electrostatic free energies were weakly correlated. This was true for both clean and organic-fouled membranes. Bacterial deposition rates were clearly influenced by an antagonistic interplay between macroscopic surface hydrophilicity and nano-scale surface roughness.

Role of specific ion interactions in seawater RO membrane fouling by alginic acid.

Organic fouling plagues many environmental membrane processes. In this study, well-controlled laboratory experiments were performed to elucidate seawater RO membrane fouling by alginic acid. Interfacial free energies derived from multiple probe liquid contact angle analyses (including different seawater matrices) correlated strongly with the rates of membrane fouling. More importantly, the Lewis acid-base interfacial free energy quantitatively described the impacts of calcium-carboxylate complex formation and predicted membrane fouling and cleaning behavior. Calcium ions made polyamide composite RO membranes (and alginic acid) more hydrophobic, enhanced the rate and extent of flux decline, and reduced the effectiveness of chemical cleaning. The implications for seawater RO membrane fouling are clear. Selective removal of calcium ions via pretreatment can reduce the gel forming ability of carboxylate rich biomacromolecules and, hence, the extent to which they foul RO membranes. In addition, RO membranes should be produced with smooth, hydrophilic interfaces comprising monopolar electron-donor functionality and no carboxylic acid residue. More broadly, this paper presents a facile approach for quantifying the impacts of specific ion interactions on aquatic colloid stability, aggregation, and deposition.

Influence of zeolite crystal size on zeolite-polyamide thin film nanocomposite membranes.

Zeolite-polyamide thin film nanocomposite membranes were coated onto polysulfone ultrafiltration membranes by interfacial polymerization of amine and acid chloride monomers in the presence of Linde type A zeolite nanocrystals. A matrix of three different interfacial polymerization chemistries and three different-sized zeolite crystals produced nanocomposite thin films with widely varying structure, morphology, charge, hydrophilicity, and separation performance (evaluated as reverse osmosis membranes). Pure polyamide film properties were tuned by changing polymerization chemistry, but addition of zeolite nanoparticles produced even greater changes in separation performance, surface chemistry, and film morphology. For fixed polymer chemistry, addition of zeolite nanoparticles formed more permeable, negatively charged, and thicker polyamide films. Smaller zeolites produced greater permeability enhancements, but larger zeolites produced more favorable surface properties; hence, nanoparticle size may be considered an additional "degree of freedom" in designing thin film nanocomposite reverse osmosis membranes. The data presented offer additional support for the hypothesis that zeolite crystals alter polyamide thin film structure when they are present during the interfacial polymerization reaction.

Influence of solute-membrane affinity on rejection of uncharged organic solutes by nanofiltration membranes.

A simple, analytical method for predicting transport of uncharged organic solutes through nanofiltration (NF) and reverse osmosis (RO) membranes is presented in this paper. The method requires characterization of key solute and membrane parameters-namely, solute size, membrane pore size, and solute-membrane affinity. All three parameters can be experimentally determined from relatively simple permeation tests and contact angle analyses. The parameters are fed into an analytical model of solute transport, which accounts for hindered convection and diffusion of solutes in the membrane pores, as well as the combined effects of steric exclusion and solute-membrane affinity on solute partitioning from the feed solution into the membrane pores. Overall model predictions for organic solute rejection agreed well with experimental data for three different solutes and two different polymeric NF membranes. Further, the model demonstrates the dramatic influence of solute-membrane affinity on organic rejection by NF and RO membranes. Solute transport predictions made assuming only steric exclusion significantly overestimated rejections for solutes with strong affinity for membrane polymers and similarly underestimated rejections for solutes that were strongly repelled by membrane polymers.

Direct observation of microbial adhesion to membranes.

Direct microscopic observation and an interfacial force model were used to better understand and control microbial adhesion to polymeric ultrafiltration membranes. The model was used to predict a "critical flux", below which cells deposited reversibly, and direct observation was used to visually quantify cell deposition and removal. In preliminary direct observation experiments, permeate reversal (backpulsing) was more effective than cross-flow hydrodynamics at removing deposited cells. In experiments conducted below the critical flux, no cell accumulation was observed over repeated forward-reverse filtration cycles; however, a small fraction of cells deposited irreversibly regardless of the flux, membrane, or solution chemistry. The fraction of irreversibly deposited cells was consistent with the equilibrium surface coverage attained without permeation (i.e., due to heterogeneous adsorption). Although steric forces were not invoked to establish a critical flux, when operating above the critical flux, a balance between permeation drag and steric repulsion appeared to determine the strength of adhesion of cells to membranes. Direct observation also confirmed that above the critical flux fouling occurred and pressure losses accumulated over several backpulse cycles, whereas below the critical flux there were no observable pressure losses or fouling.