Precise Cation Separations with Composite Cation-Exchange Membranes: Role of Base Layer Properties.

Separation of specific ions from water could enable recovery and reuse of essential metals and nutrients, but established membrane technologies lack the high-precision selectivity needed to facilitate a circular resource economy. In this work, we investigate whether the cation/cation selectivity of a composite cation-exchange membrane (CEM), or a thin polymer selective layer on top of a CEM, may be limited by the mass transfer resistance of the underlying CEM. In our analysis, we utilize a layer-by-layer technique to modify CEMs with a thin polymer selective layer (∼50 nm) that has previously shown high selectivity toward copper over similarly sized metals. While these composite membranes have a CuCl2/MgCl2 selectivity up to 33 times larger than unmodified CEMs in diffusion dialysis, our estimates suggest that eliminating resistance from the underlying CEM could further increase selectivity twofold. In contrast, the CEM base layer has a smaller effect on the selectivity of these composite membranes in electrodialysis, although these effects could become more pronounced for ultrathin or highly conductive selective layers. Our results highlight that base layer resistance prevents selectivity factors from being comparable across diffusion dialysis and electrodialysis, and CEMs with low resistance are necessary for providing highly precise separations with composite CEMs.

Low-resistance monovalent-selective cation exchange membranes prepared using molecular layer deposition for energy-efficient ion separations.

The desalination of brackish water provides water to tens of millions of people around the world, but current technologies deplete much needed nutrients from the water, which is determinantal to both public health and agriculture. A selective method for brackish water desalination, which retains the needed nutrients, is electrodialysis (ED) using monovalent-selective cation exchange membranes (MVS-CEMs). However, due to the trade-off between membrane selectivity and resistance, most MVS-CEMs demonstrate either high transport resistance or low selectivity, which increase energy consumption and hinder the use of such membranes for brackish water desalination by ED. Here, we introduce a new method for fabrication of MVS-CEMs, using molecular layer deposition (MLD) to coat CEMs with ultrathin, hybrid organic-inorganic, positively charged layers of alucone. Using MLD enabled us to precisely control and minimize the selective layer thickness, while the flexibility and nanoporosity of the alucone prevent cracking and delamination. Under conditions simulating brackish water desalination, the modified CEMs provides monovalent selectivity with negligible added resistance-thereby alleviating the selectivity-resistance trade-off. Addressing the water-energy nexus, MLD-coating enables selective brackish water desalination with minimal increase in energy consumption and opens a new path for tailoring membranes' surface properties.

Tracking SARS-CoV-2 RNA through the Wastewater Treatment Process.

Municipal sewage carries degraded and intact viral particles and RNA (ribonucleic acid) of SARS-CoV-2 (severe acute respiratory coronavirus 2), shed by COVID-19 (coronavirus disease 2019) patients, to sewage and eventually to wastewater treatment plants. Proper wastewater treatment can prevent uncontrolled discharges of the virus into the environment. However, the role of different wastewater treatment stages in reducing viral RNA concentrations is, thus far, unknown. Here, we quantified SARS-CoV-2 RNA in raw sewage and during the main stages of the activated sludge process from two wastewater treatment plants in Israel, on three different days during the 2020 COVID-19 outbreak. To reduce the detection limit, samples were concentrated prior to quantification by real-time polymerase chain reaction by a factor of 2-43 using ultrafiltration. On average, ∼1 log RNA removal was attained by each of the primary and secondary treatment steps; however, >100 copies of SARS-CoV-2 RNA/mL remained in the secondary effluents. Following chlorination, SARS-CoV-2 RNA was detected only once, likely due to an insufficient chlorine dose. Our results emphasize the capabilities and limitations of the conventional wastewater treatment process in reducing the SARS-CoV-2 RNA concentration and present preliminary evidence for the importance of tertiary treatment and chlorination in reducing dissemination of the virus to the environment.

Regressing SARS-CoV-2 Sewage Measurements Onto COVID-19 Burden in the Population: A Proof-of-Concept for Quantitative Environmental Surveillance.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is an RNA virus, a member of the coronavirus family of respiratory viruses that includes severe acute respiratory syndrome coronavirus 1 (SARS-CoV-1) and the Middle East respiratory syndrome (MERS). It has had an acute and dramatic impact on health care systems, economies, and societies of affected countries during the past 8 months. Widespread testing and tracing efforts are being employed in many countries in attempts to contain and mitigate this pandemic. Recent data has indicated that fecal shedding of SARS-CoV-2 is common and that the virus RNA can be detected in wastewater. This indicates that wastewater monitoring may provide a potentially efficient tool for the epidemiological surveillance of SARS-CoV-2 infection in large populations at relevant scales. In particular, this provides important means of (i) estimating the extent of outbreaks and their spatial distributions, based primarily on in-sewer measurements, (ii) managing the early-warning system quantitatively and efficiently, and (iii) verifying disease elimination. Here we report different virus concentration methods using polyethylene glycol (PEG), alum, or filtration techniques as well as different RNA extraction methodologies, providing important insights regarding the detection of SARS-CoV-2 RNA in sewage. Virus RNA particles were detected in wastewater in several geographic locations in Israel. In addition, a correlation of virus RNA concentration to morbidity was detected in Bnei-Barak city during April 2020. This study presents a proof of concept for the use of direct raw sewage-associated virus data, during the pandemic in the country as a potential epidemiological tool.

Tuning the Ion-Selectivity of Thin-Film Composite Nanofiltration Membranes by Molecular Layer Deposition of Alucone.

This work addresses a key challenge of tailoring the ion selectivity of a thin-film composite nanofiltration membrane to a specific application, such as water softening, without altering the water permeability. We modified the active surface of a commercial NF270 membrane by molecular layer deposition (MLD) of ethylene glycol-Al (EG-alucone). With increasing deposition cycles, we found that the MLD precursors first infiltrated and deposited in the active layer of NF270, then inflated the active layer, and finally deposited on the surface as a distinct EG-alucone layer. The deposition process changed the morphology of the membrane active layer and decreased the overall density of its fixed negative charge by embedding the positively charged EG-alucone. Filtration experiments revealed that these modifications affected the ion separation properties of the membrane without significantly hindering the water permeability. Specifically, the permeation of Na+ increased relative to that of Mg2+, as indicated by the permselectivity of Na+ salts over Mg2+ salts. The changes in permselectivities with an increasing number of MLD cycles were rationalized using the dielectric, steric, and electrostatic ion exclusion mechanisms, which are related to the membrane material, pore size, and fixed charge, respectively. These relations open a path for the rational design of nanofiltration membranes with tailored selectivity by tuning the properties of the MLD layer. Filtration results of natural brackish groundwater using the MLD modified membranes agreed with the single salt experiments. As a result, water hardness was 26% lower for the permeate obtained using the MLD-modified membranes, which were found stable even during a 24 h filtration run. These results highlight the practical potential of this approach in enhancing water softening efficiency.

Molecular insight into the interfacial chemical functionalities regulating heterogeneous calcium-arsenate nucleation.

Heterogeneous nucleation induced by natural organic matter (NOM) can lower the energy barrier for calcium arsenate (Ca-As) precipitation, which aids in immobilizing arsenate (AsⅤ). However, it remains unclear how certain chemical functionalities of NOM affect Ca-As nucleation at the molecular scale. By analyzing changes in the local supersaturation and/or interfacial energy, the present work investigates the Ca-As heterogeneous nucleation kinetics and mechanisms on functional-group-modified model surfaces. Mica surfaces modified by functional groups of amine (NH2), hydroxyl (OH), or carboxyl (COOH) through self-assembled monolayers were used to investigate how chemical functionalities affect the Ca-As heterogeneous nucleation, in which the distributions of formation kinetics and size (as measured by the change in particle height) of nucleated Ca-As particles were measured by using in situ atomic force microscopy. In a parallel analysis, a quartz-crystal microbalance with dissipation was used to detect the buildup of Ca2+ and/or HAsO42- ions at the solid-fluid interface. PeakForce quantitative nanomechanical mapping and dynamic force spectroscopy using functional-group-modified tips made it possible to calculate the binding energies holding functional groups to Ca-As particles. Nucleated Ca-As particles were characterized by using Raman spectroscopy and high-resolution transmission electron microscopy. The results indicate that the height of amorphous Ca-As particles formed on a modified mica surface may be ranked in descending order as NH2 > OH > bare mica > COOH, as determined by the buildup of Ca2+ and HAsO42- ions at the solid-fluid interface and the decrease of interfacial energy due to the functional groups. These nanoscale observations and molecular-scale determinations improve our understanding of the roles played by chemical functionalities on NOM in immobilizing dissolved As through heterogeneous nucleation in soil and water.

Phosphorous recovery from a novel recirculating aquaculture system followed by its sustainable reuse as a fertilizer.

Phosphorus (P) is an essential element for life that is introduced through feed in modern aquaculture-the fastest growing food production sector. P can also be a source of environmental contamination and eutrophication if mistreated. Fish assimilate only 20-40% of the applied P; the rest is released into the water. The goals of this research were to study the fate of P in a novel intensive near-zero discharge (<1%) recirculating aquaculture system (RAS). We also tested means to recover and reuse the removed P. Water, sludge and the microbial communities in the different treatment units of the system were analyzed. The treated sludge was tested as a potential substitute for P fertilization in a planter experiment. Of the applied P, 29.5% was recovered by fish, 69.8% was found in the fish sludge and 3.8% was released into the water as soluble reactive P. The P concentration in the fish tank remained stable, likely due to its uptake by denitrifying polyphosphate-accumulating organisms and its precipitation in the RAS's anaerobic reactor. Thus, only 1.5% of the applied P was discharged as effluent, and 69% recovered. The dominant minerals were from the apatite group, followed by the struvite family. Differences in mineral abundance between thermodynamic prediction and actual findings were most probably due to biomineralization by bacteria. Similar plant biomass was recorded for the commercial and digested-sludge fertilization treatments. Biological P removal and recovery from RAS was successfully studied and demonstrated.

Ion Transport in Laser-Induced Graphene Cation-Exchange Membrane Hybrids.

Ion-exchange membranes hybridized with laser-induced graphene (LIG) might lead to membranes with functional surface effects such as antifouling, antibacterial, or joule heating effects; however, understanding the change in the electrical properties of the membrane is essential. Here we studied LIG-modified ion-exchange polymeric membranes using electrochemical impedance spectroscopy (EIS). The conductivity of the anionic sulfonated poly(ether sulfone) membranes and the effective capacitance of the membrane-electrolyte interface were obtained by fitting the EIS spectra to an electrochemical equivalent circuit and compared with LIG-modified nonionic poly(ether sulfone) films. The transport selectivity (as the relative permeability) of counterions (K+, Na+, Mg2+, Ca2+) across the membrane was quantified using the membrane's conductivities obtained from the EIS measurements. The total ohmic resistance of the membrane was directly correlated to the polymer thickness (with negligible contribution from the conductive LIG layer), thereby establishing EIS as a rapid, low-cost, and noninvasive method to accurately probe substrate usage in LIG modification.

Microfiltration of deformable microgels.

Understanding the separation, concentration and purification processes of soft nanoparticles is essential for numerous applications in water filtration, bioprocessing and blood separation. Here we report unique translocation and rejection features of sub-micron sized microgels during frontal filtration using membranes having micron-sized porosity. Simultaneously measuring the increase in hydraulic resistance and electrical impedance change allows us to clearly distinguish two deposition phases: (a) microgel accumulation within the depth of the membrane porosity and (b) subsequent formation of a thin gel layer on the membrane surface. Such distinction is impossible using only classical hydraulic resistance analysis. The methodology only requires the ratio of microgel to solution conductivity as an input parameter.

Modeling pH variation in reverse osmosis.

The transport of hydronium and hydroxide ions through reverse osmosis membranes constitutes a unique case of ionic species characterized by uncommonly high permeabilities. Combined with electromigration, this leads to complex behavior of permeate pH, e.g., negative rejection, as often observed for monovalent ions in nanofiltration of salt mixtures. In this work we employed a rigorous phenomenological approach combined with chemical equilibrium to describe the trans-membrane transport of hydronium and hydroxide ions along with salt transport and calculate the resulting permeate pH. Starting from the Nernst-Planck equation, a full non-linear transport equation was derived, for which an approximate solution was proposed based on the analytical solution previously developed for trace ions in a dominant salt. Using the developed approximate equation, transport coefficients were deduced from experimental results obtained using a spiral wound reverse osmosis module operated under varying permeate flux (2-11 µm/s), NaCl feed concentrations (0.04-0.18 M) and feed pH values (5.5-9.0). The approximate equation agreed well with the experimental results, corroborating the finding that diffusion and electromigration, rather than a priori neglected convection, were the major contributors to the transport of hydronium and hydroxide. The approach presented here has the potential to improve the predictive capacity of reverse osmosis transport models for acid-base species, thereby improving process design/control.

Reducing the specific energy consumption of 1st-pass SWRO by application of high-flux membranes fed with high-pH, decarbonated seawater.

A new operational approach is presented, which has the potential to substantially cut down on the energy and cost demand associated with seawater reverse osmosis (SWRO) desalination, without changing the currently-installed infrastructure. The approach comprises acidification/decarbonation of the feed seawater followed by high-pH single RO pass using high-flux membranes. Since the limitation imposed by CaCO3(s) precipitation is overcome, the recovery ratio can be significantly increased. This work presents a new operational concept aimed at maximizing the benefits that can be obtained from new low-energy RO membranes available on the market. Results obtained from operating a pilot RO system revealed that following an acidification and decarbonation step, recovery ratio of 56% could be practically attained, along with effluent TDS and boron concentrations of 375 and 0.3 mg/l, respectively (feed water pH was adjusted to pH9.53 following the decarbonation step). The specific energy consumption (SEC) of this operation was calculated to be 5%-10% lower than the SEC typically associated with "conventional" SWRO operation. Two further scenarios were theoretically considered, under which the limiting operational parameter became Mg(OH)2(s) and BaSO4(s) precipitation. It was concluded that despite the fact that higher recovery ratios could be obtained, the high pressure required in these scenarios made them less appealing from both the SEC and cost standpoints. The normalized cost of the suggested approach was found to be ∼$0.07 ± 0.02/m(3) cheaper than the currently-practiced SWRO approach for obtaining product water characterized by TDS < 500 and B < 0.5 mg/l.

Predicting the Rejection of Major Seawater Ions by Spiral-Wound Nanofiltration Membranes.

Seawater nanofiltration (SWNF) generates a softened permeate stream and a retentate stream in which the multivalent ions accumulate, offering opportunities for practical utilization of both streams. This study presents an approach to simulation of SWNF including all major seawater ions (Na(+), Cl(-), Ca(2+), Mg(2+), and SO4(2-)) based on the Nernst-Planck equation, and uses it for permeate and retentate streams composition prediction. The number of degrees of freedom in the system was reduced by assuming a very high ionic permeability for Na(+), which only weakly affected the other parameters in the system. Two alternatives were examined to analyze the importance of concentration dependence of ion permeabilities: The assumption of constant ion permeabilities resulted in a reasonable fit with experimental data. However, for the permeate composition the overall fit was significantly improved (P < 0.0001) when the permeabilities of Ca(2+) and Mg(2+) were allowed to depend on the ratio of their total concentration to Na(+). This type of dependence emphasizes the strong interaction of divalent ions with the membrane and its effect on the membrane fixed charge through screening or charge reversal. When this effect was included, model predictions closely matched the experimental results obtained, corroborating the phenomenological approach proposed in this study.

A new algorithm for design, operation and cost assessment of struvite (MgNH4PO4) precipitation processes.

Deliberate struvite (MgNH4PO4) precipitation from wastewater streams has been the topic of extensive research in the last two decades and is expected to gather worldwide momentum in the near future as a P-reuse technique. A wide range of operational alternatives has been reported for struvite precipitation, including the application of various Mg(II) sources, two pH elevation techniques and several Mg:P ratios and pH values. The choice of each operational parameter within the struvite precipitation process affects process efficiency, the overall cost and also the choice of other operational parameters. Thus, a comprehensive simulation program that takes all these parameters into account is essential for process design. This paper introduces a systematic decision-supporting tool which accepts a wide range of possible operational parameters, including unconventional Mg(II) sources (i.e. seawater and seawater nanofiltration brines). The study is supplied with a free-of-charge computerized tool (http://tx.technion.ac.il/~agrengn/agr/Struvite_Program.zip) which links two computer platforms (Python and PHREEQC) for executing thermodynamic calculations according to predefined kinetic considerations. The model can be (inter alia) used for optimizing the struvite-fluidized bed reactor process operation with respect to P removal efficiency, struvite purity and economic feasibility of the chosen alternative. The paper describes the algorithm and its underlying assumptions, and shows results (i.e. effluent water quality, cost breakdown and P removal efficiency) of several case studies consisting of typical wastewaters treated at various operational conditions.

Accurate and self-consistent procedure for determining pH in seawater desalination brines and its manifestation in reverse osmosis modeling.

Measuring and modeling pH in concentrated aqueous solutions in an accurate and consistent manner is of paramount importance to many R&D and industrial applications, including RO desalination. Nevertheless, unified definitions and standard procedures have yet to be developed for solutions with ionic strength higher than ∼0.7 M, while implementation of conventional pH determination approaches may lead to significant errors. In this work a systematic yet simple methodology for measuring pH in concentrated solutions (dominated by Na(+)/Cl(-)) was developed and evaluated, with the aim of achieving consistency with the Pitzer ion-interaction approach. Results indicate that the addition of 0.75 M of NaCl to NIST buffers, followed by assigning a new standard pH (calculated based on the Pitzer approach), enabled reducing measured errors to below 0.03 pH units in seawater RO brines (ionic strength up to 2 M). To facilitate its use, the method was developed to be both conceptually and practically analogous to the conventional pH measurement procedure. The method was used to measure the pH of seawater RO retentates obtained at varying recovery ratios. The results matched better the pH values predicted by an accurate RO transport model. Calibrating the model by the measured pH values enabled better boron transport prediction. A Donnan-induced phenomenon, affecting pH in both retentate and permeate streams, was identified and quantified.