The Minus Approach Can Redefine the Standard of Practice of Drinking Water Treatment.

Chlorine-based disinfection for drinking water treatment (DWT) was one of the 20th century's great public health achievements, as it substantially reduced the risk of acute microbial waterborne disease. However, today's chlorinated drinking water is not unambiguously safe; trace levels of regulated and unregulated disinfection byproducts (DBPs), and other known, unknown, and emerging contaminants (KUECs), present chronic risks that make them essential removal targets. Because conventional chemical-based DWT processes do little to remove DBPs or KUECs, alternative approaches are needed to minimize risks by removing DBP precursors and KUECs that are ubiquitous in water supplies. We present the "Minus Approach" as a toolbox of practices and technologies to mitigate KUECs and DBPs without compromising microbiological safety. The Minus Approach reduces problem-causing chemical addition treatment (i.e., the conventional "Plus Approach") by producing biologically stable water containing pathogens at levels having negligible human health risk and substantially lower concentrations of KUECs and DBPs. Aside from ozonation, the Minus Approach avoids primary chemical-based coagulants, disinfectants, and advanced oxidation processes. The Minus Approach focuses on bank filtration, biofiltration, adsorption, and membranes to biologically and physically remove DBP precursors, KUECs, and pathogens; consequently, water purveyors can use ultraviolet light at key locations in conjunction with smaller dosages of secondary chemical disinfectants to minimize microbial regrowth in distribution systems. We describe how the Minus Approach contrasts with the conventional Plus Approach, integrates with artificial intelligence, and can ultimately improve the sustainability performance of water treatment. Finally, we consider barriers to adoption of the Minus Approach.

Modulating the Asymmetry of the Active Layer in Pursuit of Nanofiltration Selectivity via Differentiating Interfacial Reactions of Piperazine.

Nanofiltration (NF), highly prospective for drinking water treatment, faces a challenge in simultaneously removing emerging contaminants while maintaining mineral salts, particularly divalent cations. To overcome this challenge, NF membranes possessing small pores concomitant with highly negatively charged surfaces were synthesized via a two-step fabrication strategy. The key is to generate a polyamide active layer having a loose and carboxyl group-abundant segment on top and a dense barrier segment underneath. This was achieved by restrained interfacial polymerization between trimesoyl chloride and partly protonated piperazine to form a highly depth-heterogeneous polyamide network, followed by second amidation in an organic environment to remove untethered polyamide fragments and associate malonyl chlorides with reserved amine groups to introduce more negative charges. Most importantly, on first-principle engineering the spatial architecture of the polyamide layer, amplifying asymmetric charge distribution was paired with the thinning of the vertical structure. The optimized membrane exhibits high salt/organic rejection selectivity and water permeance superior to most NF membranes reported previously. The rejections of eight emerging contaminants were in the range of 66.0-94.4%, much higher than the MgCl2 rejection of 41.1%. This new fabrication strategy, suitable for various diacyl chlorides, along with the new membranes so produced, offers a novel option for NF in potable water systems.

MXene Composite Membranes with Enhanced Ion Transport and Regulated Ion Selectivity.

Two-dimensional (2D) material-based membranes are promising candidates for various separation applications. However, the further enhancement of membrane ion conductance is difficult, and the regulation of membrane ion selectivity remains a challenge. Here, we demonstrate the facile fabrication of MXene composite membranes by incorporating spacing agents that contain SO3H groups into the MXene interlayers. The synthesized membrane shows enhanced ion conductance and ion selectivity. Subsequently, the membranes are utilized for salinity gradient power (SGP) generation and lithium-ion (Li+) recovery. The membrane containing poly(sodium 4-styrenesulfonate) (PSS) as the spacing agent shows a much higher power density for SGP generation as compared to the pristine MXene membrane. Using artificial seawater and river water, the power density reaches 1.57 W/m2 with a testing area of 0.24 mm2. Also, the same membrane shows Li+/Na+ and Li+/K+ selectivities of 2.5 and 3.2, respectively. The incorporation of PSS increases both the size and charge density of the nanochannels inside the membrane, which is beneficial for ion conduction. In addition, the density functional theory (DFT) calculation shows that the binding energy between Li+ and the SO3H group is lower than other alkali ion metals, and this might be one major reason why the membrane possesses high Li+ selectivity. This study demonstrates that incorporating spacing agents into the 2D material matrix is a viable strategy to enhance the performance of the 2D material-based membranes. The results from this study can inspire new membrane designs for emerging applications including energy harvesting and monovalent ion recovery.

Capillary-Assisted Fabrication of Thin-Film Nanocomposite Membranes for Improved Solute-Solute Separation.

Efficient separation of harmful contaminants (e.g., per- and polyfluoroalkyl substances, PFASs) from valuable components (water and nutrients) is essential to the resource recovery from domestic wastewater for agricultural purposes. Such selective recovery requires precise separation at the angstrom scale. Although nanofiltration (NF) has the potential to achieve solute-solute separation, the state-of-the-art polyamide (PA) membranes are typically constrained by limited precision of solute-solute selectivity and their well-documented permeability-selectivity trade-off. Herein, we present a novel capillary-assisted interfacial polymerization (CAIP) approach to generate metal-organic framework (MOF)-PA nanocomposite membranes with reduced surface charges and more uniform pore sizes that favor solute selectivity by enhanced size exclusion. By uniquely regulating the PA-MOF interactions using the capillary force, CAIP results in effective exposure of MOF nanochannels on the membrane surface and a PA matrix with a high cross-linking gradient in the vertical direction, both of which contribute to an exceptional water permeance of ∼18.7 LMH/bar and an unprecedentedly high selectivity between nutrient ions and PFASs. Our CAIP approach breaks new ground for utilizing nanoparticles with nanochannels in fabricating the next-generation, fit-for-purpose NF membranes for improved solute-solute separations.

Revolutionizing Membrane Design Using Machine Learning-Bayesian Optimization.

Polymeric membrane design is a multidimensional process involving selection of membrane materials and optimization of fabrication conditions from an infinite candidate space. It is impossible to explore the entire space by trial-and-error experimentation. Here, we present a membrane design strategy utilizing machine learning-based Bayesian optimization to precisely identify the optimal combinations of unexplored monomers and their fabrication conditions from an infinite space. We developed ML models to accurately predict water permeability and salt rejection from membrane monomer types (represented by the Morgan fingerprint) and fabrication conditions. We applied Bayesian optimization on the built ML model to inversely identify sets of monomer/fabrication condition combinations with the potential to break the upper bound for water/salt selectivity and permeability. We fabricated eight membranes under the identified combinations and found that they exceeded the present upper bound. Our findings demonstrate that ML-based Bayesian optimization represents a paradigm shift for next-generation separation membrane design.

Fit-for-Purpose Design of Nanofiltration Membranes for Simultaneous Nutrient Recovery and Micropollutant Removal.

Domestic wastewater is a valuable reservoir of nutrients such as nitrogen and phosphorus. However, the presence of emerging micropollutants (EMPs) hinders its applications in resource recovery. In this study, we designed and fabricated a novel thin-film composite polyamide membrane, which enables highly selective nanofiltration (NF) that removes EMPs effectively while preserving valuable nutrients in the permeate. By incorporating polyethylenimine as an additional monomer to piperazine and surfactant sodium dodecyl sulfate in interfacial polymerization, we precisely tuned membrane pore size, pore size distribution, and surface charge. The resultant NF membrane achieved desirable solute-solute selectivity between EMPs (rejection rate > 75%) and nutrient N and P ions (rejection rate < 25%). By applying a modified Donnan steric pore model with dielectric exclusion, which takes membrane pore size distribution into consideration, we demonstrate the synergistic effect of membrane pore size, pore size distribution, and surface charge in regulating membrane solute-solute selectivity. Designing solute-solute selective NF membranes for fit-for-purpose wastewater treatment has great potential to improve the flexibility of membrane technologies that can convert wastewater streams to valuable water and nutrient resources.

Differentiating Solutes with Precise Nanofiltration for Next Generation Environmental Separations: A Review.

Selective removal or enrichment of targeted solutes including micropollutants, valuable elements, and mineral scalants from complex aqueous matrices is both challenging and pivotal to the success of water purification and resource recovery from unconventional water resources. Membrane separation with precision at the subnanometer or even subangstrom scale is of paramount importance to address those challenges via enabling "fit-for-purpose" water and wastewater treatment. So far, researchers have attempted to develop novel membrane materials with precise and tailored selectivity by tuning membrane structure and chemistry. In this critical review, we first present the environmental challenges and opportunities that necessitate improved solute-solute selectivity in membrane separation. We then discuss the mechanisms and desired membrane properties required for better membrane selectivity. On the basis of the most recent progress reported in the literature, we examine the key principles of material design and fabrication, which create membranes with enhanced and more targeted selectivity. We highlight the important roles of surface engineering, nanotechnology, and molecular-level design in improving membrane selectivity. Finally, we discuss the challenges and prospects of highly selective NF membranes for practical environmental applications, identifying knowledge gaps that will guide future research to promote environmental sustainability through more precise and tunable membrane separation.

An MIMO Radar System Based on the Sparse-Array and Its Frequency Migration Calibration Method.

In this paper, a Multiple Input Multiple Output (MIMO) radar system based on a sparse-array is proposed. In order to reduce the side-lobe level, a genetic algorithm (GA) is used to optimize the array arrangement. To reduce the complexity of the system, time-division multiplexing (TDM) technology is adopted. Since the signals are received in different periods, a frequency migration will emerge if the target is in motion, which will lead to the lower direction-of-arrival (DOA) performance of the system. To solve this problem, a stretching transformation method in the fast-frequency slow-time domain is proposed, in order to eliminate frequency migration. Only minor adjustments need to be implemented for the signal processing, and the root-mean-square error (RMSE) of the DOA estimation will be reduced by about 90%, compared with the one of an uncalibrated system. For example, a uniform linear array (ULA) MIMO system with 2 transmitters and 20 receivers can be replaced by the proposed system with 2 transmitters and 12 receivers, achieving the same DOA performance. The calibration formulations are given, and the simulation results of the automotive radar system are also provided, which validate the theory.

Controlled TiO2 Growth on Reverse Osmosis and Nanofiltration Membranes by Atomic Layer Deposition: Mechanisms and Potential Applications.

Enhancing the chemical and physical properties of the polyamide active layer of thin-film composite (TFC) membranes by surface coating is a goal long-pursued. Atomic layer deposition (ALD) has been proposed as an innovative approach to deposit chemically robust metal oxides onto membrane surfaces due to its unique capability to control coating conformality and thickness with atomic scale precision. This study examined the potential to coat the surface of TFC reverse osmosis (RO) and nanofiltration (NF) membranes via ALD of TiO2. Our results suggest that the optimal ALD conditions, the film growth kinetics, and the depth of deposition are different for RO and NF membranes due to the different diffusive transport of ALD precursors through the membrane pores. The TiO2 coating mainly located at the surface of the RO membrane; in contrast, the TiO2 coating extended to the depth of the NF membrane. The TiO2 coating degraded membrane water permeability and salt rejection beyond 10 cycles of ALD, the condition commonly employed in previous ALD-based membrane modification studies. Instead, this study showed that with fewer than 10 cycles, the TiO2 coating of RO membrane increased the membrane surface charge without negatively impacting water permeability and salt rejection. For the NF membranes, the coating of TiO2 inside their pores led to the tuning of pore sizes and increased the rejection of selected solutes.

Influence of the Exclusion-Enrichment Effect on Ion Transport in Two-Dimensional Molybdenum Disulfide Membranes.

Two-dimensional (2D) nanosheet membranes have been widely studied for water and wastewater treatment. However, mass transport inside 2D nanosheet membranes is far from being fully understood, and suitable applications of these membranes are yet to be identified. In this study, we investigate ion transport inside a 2D molybdenum disulfide (MoS2) membrane by combining experimental results with numerical modeling. Specifically, we analyze the influence of the electrical double layer (EDL) extension on ion diffusion in the MoS2 membrane, and a parameter called the exclusion-enrichment coefficient (ß) is introduced to quantify how the electrostatic interaction between the coions and the EDL can affect the ion diffusion. Using the model developed in this study, the ß values under different experimental conditions (feed solution concentration and applied hydraulic pressure) are calculated. The results show that coion diffusion inside the membrane can be retarded since ß is smaller than one. Furthermore, the underlying mechanism is explored by theoretically estimating the radial ion concentration and electrical potential distributions across the membrane nanochannel. In addition, we find that convective mass transport can weaken the exclusion-enrichment effect by increasing ß. Based on the results in this study, the potential applications and feasible membrane design strategies of 2D nanosheet membranes are discussed.

Impacts of Metal-Organic Frameworks on Structure and Performance of Polyamide Thin-Film Nanocomposite Membranes.

Metal-organic frameworks (MOFs), a class of hybrid organic-inorganic materials, have recently attracted tremendous interests in the fabrication of thin-film nanocomposite (TFN) membranes with exceptional permselectivity. However, the structure-performance relationship of such membranes, which is a function of both MOF type and membrane fabrication procedure, has not been elucidated in the literature. In this study, three types of hydro-stable MOFs, namely, MIL-53(Al), NH2-UiO-66, and ZIF-8, were used to fabricate TFN nanofiltration membranes via both blending (BL) and preloading interfacial polymerization methods. Results show that the incorporation of MOFs could enhance water permeability of TFN membranes to 7.2 L/(m2·h·bar) at most ( TFNNH2-UiO-66-BL-0.10%), about 1.3 times of the corresponding thin-film composite membranes, without sacrificing their selectivity to reject NaCl (>40%) and xylose (>65%). Membrane characterization revealed that MOFs decreased the cross-linking degree while increasing the membrane thickness, surface negative charge, and roughness of the polyamide active layer. MIL-53(Al) were found to bind with polyamide via reacting with piperazine, whereas weaker polyamide-MOF interactions were observed for NH2-UiO-66 and ZIF-8. This difference, along with the hydrophilicity of MOF particles, explained the varied permselectivity of different TFN membranes. Compared to pristine polyamide membranes, the TFN membranes demonstrated higher or comparable efficiencies in removing a set of six pharmaceuticals (PhACs), which were determined by the molecular properties of PhACs and membrane structure. The findings of this study deepen our understanding of the roles that MOFs play in regulating membrane performance, promoting molecular design of MOF-incorporated TFN membranes via precise control of MOF-polymer interactions.

Increased serum pentraxin-3 level predicts poor prognosis in patients with colorectal cancer after curative surgery, a cohort study.

Pentraxin-3 (PTX3) is a glycoprotein involved in inflammation and immune regulation of cancer. The aim of this study was to evaluate the serum PTX3 level in patients with colorectal cancer (CRC) and analyze its prognostic significance.A total of 263 consecutive patients underwent radical resection for primary CRC and 126 healthy controls were enrolled in this study. Serum PTX3 level was measured within the day before surgery though enzyme-linked immunosorbent assays, comparing with the level of healthy control. Baseline demographic and clinical characteristics were recorded. The association between serum PTX3 level and survival outcome was analyzed by the Kaplan-Meier with Log-Rank test and Cox regression methods.Mean serum PTX3 level in CRC patients was higher than that of healthy control (13.8 ±â€Š3.2ng/mL versus 3.3 ±â€Š1.2ng/mL, P < .001). Finally, 55 (20.9%) patients out of all 263 patients studied had died during following-up period. All patients were divided into 2 groups using the optimal cutoff value (12.6 ng/mL) of PTX3 level using a sensitivity of 68.0% and a specificity of 71.7% as optimal conditions from receiver operating curve analysis. Patients with a PTX3≥12.6ng/mL had poorer 5 years overall survival rate (76.6% versus 67.8%, P = .025) patients with a PTX3 < 12.6ng/mL in univariate analysis and serum PTX3 level also been confirmed as an independent predictor for survival for CRC in multivariate analysis (Hazard ratio, 1.468; 95% [confidence interval] CI, 1.081-1.976; P < .001).Serum PTX3 level can serve as an independent prognostic biomarker for CRC patients after curative resection.

Dewatering of Chlorella pyrenoidosa using diatomite dynamic membrane: filtration performance, membrane fouling and cake behavior.

The diatomite dynamic membrane (DDM) was utilized to dewater Chlorella pyrenoidosa of 2 g dry weight/L under continuous-flow mode, whose ultimate algae concentration ranged from 43 g to 22 g dry weight/L of different culture time. The stable flux of DDM could reach 30 L/m(2) h over a 24 h operation time without backwash. Influences of extracellular organic matters (EOM) on filtration behavior and membrane fouling were studied. The DDM was divided into three sub-layers, the slime layer, the algae layer and the diatomite layer from the outside to the inside of the cake layer based on components and morphologies. It was found that EOM caused membrane fouling by accumulating in the slime and algae layers. The DDM intercepted polysaccharides, protein-like substances, humic-like substances and some low-MW organics. Proteins were indicated the major membrane foulants with increased protein/polysaccharide ratio from the slime layer to the diatomite layer as culture time increased. This method could be applied to subsequent treatment of microalgae coupling technology of wastewater treatment or microalgae harvesting for producing biofuel.