Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me2NH2]V3O7 is predominantly upheld by the H-bond interaction between anionic framework [V3O7]nn- and intercalated [Me2NH2]+. The [Me2NH2]+ within [Me2NH2]V3O7 can be readily exchanged with UO22+. [Me2NH2]V3O7 exhibits high exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO22+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me2NH2]V3O7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me2NH2]V3O7 can also efficiently separate UO22+ from Cs+ or Sr2+ achieving the highest separation factors (SFU/Cs of 589 and SFU/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO22+ and [V3O7]nn-, whereas the ion exchange rate is influenced by the mobility of UO22+ and [Me2NH2]+. Our experimental findings indicate that [Me2NH2]V3O7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

Enhancing selective ammonium transport in membrane electrochemical systems.

Recovering ammonia nitrogen from wastewater is a sustainable strategy that simultaneously addresses both nitrogen removal and fertilizer production. Membrane electrochemical system (MES), which utilizes electrochemical redox reactions to transport ammonium ions through cation exchange membranes, has been considered as an effective technology for ammonia recovery from wastewater. In this study, we develop a mathematical model to systematically investigate the impact of co-existing ions on the transport of ammonium (NH4+) ions in MES. Our analysis elucidates the importance of pH values on both the NH4+ transport and inert ion (Na+) transport. We further comprehensively assess the system performance by varying the concentration of Na+ in the system. We find that while the inert cation in the initial anode compartment competes with NH4+ transport, NH4+ dominates the cation transport in most cases. The transport number of Na+ surpasses NH4+ only if the fraction of Na+ to total cation is extremely high (>88.5%). Importantly, introducing Na+ ions into the cathode compartment significantly enhances the ammonia transport due to the Donnan dialysis. The analysis of selective ion transport provides valuable insights into optimizing both selectivity and efficiency in ammonia recovery from wastewater.

A simple method to prepare anion exchange membrane by PVA/EVOH/MIDA for acid recovery by diffusion dialysis.

Given the substantial environmental pollution from industrial expansion, environmental protection has become particularly important. Nowadays, anion exchange membranes (AEMs) are widely used in wastewater treatment. With the use of polyvinyl alcohol (PVA), ethylene-vinyl alcohol (EVOH) copolymer, and methyl iminodiacetic acid (MIDA), a series of cross-linked AEMs were successfully prepared using the solvent casting technique, and the network structure was formed in the membranes due to the cross-linking reaction between PVA/EVOH and MIDA. Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy were used to analyze the prepared membranes. At the same time, its comprehensive properties which include water uptake, linear expansion rate, ion exchange capacity, thermal stability, chemical stability, and mechanical stability were thoroughly researched. In addition, diffusion dialysis performance in practical applications was also studied in detail. The acid dialysis coefficient (UH+) ranged from 10.2 to 35.6 × 10-3 m/h. Separation factor (S) value ranged from 25 to 38, which were all larger than that of the commercial membrane DF-120 (UH+: 8.5 × 10-3 m/h, S: 18.5). The prepared membranes had potential application value in acid recovery.

Site-directed mutagenesis at the Glu78 in Ec-NhaA transporter impacting ion exchange: a biophysical study.

Na+/H+ antiporters facilitate the exchange of Na+ for H+ across the cytoplasmic membrane in prokaryotic and eukaryotic cells. These transporters are crucial to maintain the homeostasis of sodium ions, consequently pH, and volume of the cells. Therefore, sodium/proton antiporters are considered promising therapeutic targets in humans. The Na+/H+ antiporter in Escherichia coli (Ec-NhaA), a prototype of cation-proton antiporter (CPA) family, transports two protons and one sodium (or Li+) in opposite direction. Previous mutagenesis experiments on Ec-NhaA have proposed Asp164, Asp163, and Asp133 amino acids with the significant implication in functional and structural integrity and create site for ion-binding. However, the mechanism and the sites for the binding of the two protons remain unknown and controversial which could be critical for pH regulation. In this study, we have explored the role of Glu78 in the regulation of pH by Ec-NhaA. Although we have created various mutants, E78C has shown a considerable effect on the stoichiometry of NhaA and presented comparable phenotypes. The ITC experiment has shown the binding of ~ 5 protons in response to the transport of one lithium ion. The phenotype analysis on selective medium showed a significant expression compared to WT Ec-NhaA. This represents the importance of Glu78 in transporting the H+ across the membrane where a single mutation with Cys amino acid alters the number of H+ significantly maintaining the activity of the protein.

Mechanistic studies of adsorption and ion exchange of Si(OH)4 molecules on the surface of scorodites.

Scorodites are commonly used for arsenic immobilization, and it is also the main component of arsenic bearing tailings. Alkali-activated geopolymers are commonly used to landfill arsenic-bearing minerals. However, there no previous studies have explored the interaction between geopolymer molecules and the surface of scorodite. In this paper, Si(OH)4 as a monomer molecule of geopolymer, the mechanism of adsorption and 'ion exchange' between Si(OH)4 molecule and the surface of scorodite during alkali-activation is studied. Results show that the Fe-terminated scorodite (010) surface has high stability. Si(OH)4 are more easily adsorbed on the hollow site of an Fe-terminated scorodite (010) surface, which is described as chemisorption. Compared with Si(OH)4, NaOH is easier to adsorb on an Fe-terminated scorodite (010) surface. The co-adsorption of NaOH and Si(OH)4 on the Fe-terminated scorodite (010) surface was studied, and also belongs to chemical adsorption. When the hydroxyl binds to the As atom, the adsorbed Si(OH)4 is more likely to undergo an 'ion exchange' reaction with the surface, and the reaction is barrierless. The intermediate As(OH)4 produced by the 'ion exchange' reaction can be deprotonated to form an arsenate molecule, which can occur spontaneously. This work reveals that the interaction mechanism of geopolymer molecules on surface of scorodite.

Selective adsorption in ion exchange membranes: The effect of solution ion composition on ion partitioning.

Electrodialysis is a water desalination technology that enables selective separation of ions, making it a promising solution for sustainable water reuse. The selectivity of the process is mainly determined by the properties of ion exchange membranes that can vary depending on the composition of ions in water, such as water uptake and charge density. In this work, we studied selective adsorption of Na+ and K+ ions in various ion exchange membranes considering the effect of solution ion composition on membrane water volume fraction. For that purpose, we conducted membrane adsorption experiments using solutions with Na+ and K+ ions with different ion compositions including Li+, Ca2+ or Mg2+ ions at different concentrations (0.001 - 0.25 M). The experiments showed that with the total ion concentration and the amount of divalent ions in solution, the membrane water volume fraction decreases while the selective adsorption of the smaller (hydrated) K+ ions over the Na+ ions in the membrane increases. We developed a theoretical framework based on Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) theory to describe the effect of membrane water volume fraction on selective adsorption of the ions by including volumetric effects, such as size exclusion. The developed framework was used to describe ion partitioning results of the membrane adsorption experiments. In addition, the effect of solution ion composition on selective ion removal during electrodialysis operation was evaluated using experimental data and theoretical calculations. The results of this study show that considering volumetric effects can improve the ion partitioning description in ion exchange membranes for solutions with various ion compositions.

Cutting-edge technologies and relevant reaction mechanism difference in treatment of long- and short-chain per- and polyfluoroalkyl substances: A review.

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants. Compared with short-chain PFAS, long-chain PFAS are more hazardous. Currently, little attention has been paid to the differences in reaction mechanisms between long-chain and short-chain PFAS. This pressing concern has prompted studies about eliminating PFAS and revealing the mechanism difference. The reaction rate and reaction mechanism of each technology was focused on, including (1) adsorption, (2) ion exchange (IX), (3) membrane filtration, (4) advanced oxidation, (5) biotransformation, (6) novel functional material, and (7) other technologies (e.g. ecological remediation, hydrothermal treatment (HT), mechanochemical (MC) technology, micro/nanobubbles enhanced technology, and integrated technologies). The greatest reaction rate k of photocatalysis for long- and short-chain PFAS high up to 63.0 h-1 and 19.7 h-1, respectively. However, adsorption, membrane filtration, and novel functional material remediation were found less suitable or need higher operation demand for treating short-chain PFAS. Ecological remediation is more suitable for treating natural waterbody for its environmentally friendly and fair reaction rate. The other technologies all showed good application potential for both short- and long-chain PFAS, and it was more excellent for long-chain PFAS. The long-chain PFAS can be cleavaged into short-chain PFAS by C-chain broken, -CF2 elimination, nucleophilic substitution of F-, and HF elimination. Furthermore, the application of each type of technology was novelly designed; and suggestions for the future development of PFAS remediation technologies were proposed.

In situ potassium and hydrogen ion exchange into a cubic zirconium silicate microporous material.

The selective separation of ions from aqueous systems, and even in the human body, is a crucial to overall environmental management and health. Nanoporous materials are widely known for their selective removal of cations from aqueous media, and therefore have been targeted for use as a pharmaceutical to treat hyperkalemia. This study investigated the detailed crystallographic molecular mechanisms that control the potassium ion selectivity in the nanoporous cubic zirconium silicate (CZS) related materials. Using time-resolved in situ Raman spectroscopy and time-resolved in situ X-ray diffraction, the selectivity mechanisms were determined to involve a synchronous cation-cation repulsion process that serves to open a favorable coordination bonding environment for potassium, not unlike the ion selectivity filter process found in potassium ion channels in proteins. Enhancement of ion exchange was observed when the CZS material was in a partial protonated state (≈3:1 Na:H), causing an expansion of the unit-cell volume, enlargement of the 7 member-ring window, and distortion of framework polyhedra, which allowed increased accessibility to the cage structures and resulted in rapid irreversible potassium ion exchange.

Evidence from experiments, modeling, and field observations for effects of increased salinization on re-distribution of sediment base cations in Taihu Lake, China.

Taihu Lake, the third largest freshwater lake in China, has experienced rapid salinization in the past decades; however, little is known about the impact of sodium (Na) on ion exchange in the lake environment. To explore the potential effect of increased Na on the migration of base cations (Ca and Mg) and resulting redistribution between the water and sediment, we used the adsorption-exchange experiment, MINTEQ modeling to explore the cation exchange induced by high Na input, and its impact on the redistribution of Ca and Mg in Taihu different media. The results indicated that exchanged quantity of Ca and Mg increased with time, and the exchange process reached 90% during 0-4 h and reached equilibrium after 24 h under 100 mg/L Na (the maximum Na concentration in Taihu sediment pore water). Our MINTEQ modeled result indicated that the exchanged quantity of Ca and Mg increased with the increasing Na concentration, with Ca being preferably exchanged over Mg at the same Na concentration. The MINTEQ model further predicted that, in the Taihu lake environment, the exchange adsorption would reach the equilibrium at the concentration of 6000 mg/L Na, with exchanged Ca2+ and Mg2+ accounting for 47% and 55% of the total exchangeable Ca and Mg in the sediment, respectively. Although current Na-induced exchange in the Taihu lake has been far from the equilibrium, the MINTEQ result confirmed the existence of this reaction and predicted the potential redistribution of base cations or Ca/Mg ratio in the lake sediment and water phase with further Na increase. Furthermore, our field observations not only confirmed the existence of Na-induced cation exchange in this lake environment but also were generally in agreement with our experimental and modeled results. The increased salinization-induced ion exchange would alter the re-distribution of base cations and the resulting potential ecosystem consequences should be given close attention in this large freshwater lake.

Novel Fluorinated Anion Exchange Membranes Based on Poly(Pentafluorophenyl-Carbazole) with High Ionic Conductivity and Alkaline Stability for Fuel Cell Applications.

Constructing good microphase separation structures by designing different polymer backbones and ion-conducting groups is an effective strategy for improving the ionic conductivity and chemical stability of anion exchange membranes (AEMs). In this study, a series of AEMs based on the poly(pentafluorophenylcarbazole) backbone grafted with different cationic groups are designed and prepared to construct well-defined microphase separation morphology and improve the trade-off between the properties of AEMs. Highly hydrophobic fluorinated backbone and alkyl spaces enhance phase separation and construct interconnected hydrophilic channels for anion transport. The ionic conductivity of the PC-PF-QA membrane is 123 mS cm-1 at 80 °C, and the ionic conductivity of the PC-PF-QA membrane decreased by only 6% after 960 h of immersion at 60 °C in 1 M NaOH aqueous solution. The maximum peak power density of the single cell based on PC-PF-QA is 214 mW cm-2 at 60 °C.

Mobility of Condensed Counterions in Ion-Exchange Membranes: Application of Screening Length Scaling Relationship in Highly Charged Environments.

Ion-exchange membranes (IEMs) are widely used in water, energy, and environmental applications, but transport models to accurately simulate ion permeation are currently lacking. This study presents a theoretical framework to predict ionic conductivity of IEMs by introducing an analytical model for condensed counterion mobility to the Donnan-Manning model. Modeling of condensed counterion mobility is enabled by the novel utilization of a scaling relationship to describe screening lengths in the densely charged IEM matrices, which overcame the obstacle of traditional electrolyte chemistry theories breaking down at very high ionic strength environments. Ionic conductivities of commercial IEMs were experimentally characterized in different electrolyte solutions containing a range of mono-, di-, and trivalent counterions. Because the current Donnan-Manning model neglects the mobility of condensed counterions, it is inadequate for modeling ion transport and significantly underestimated membrane conductivities (by up to ≈5× difference between observed and modeled values). Using the new model to account for condensed counterion mobilities substantially improved the accuracy of predicting IEM conductivities in monovalent counterions (to as small as within 7% of experimental values), without any adjustable parameters. Further adjusting the power law exponent of the screen length scaling relationship yielded reasonable precision for membrane conductivities in multivalent counterions. Analysis reveals that counterions are significantly more mobile in the condensed phase than in the uncondensed phase because electrostatic interactions accelerate condensed counterions but retard uncondensed counterions. Condensed counterions still have lower mobilities than ions in bulk solutions due to impedance from spatial effects. The transport framework presented here can model ion migration a priori with adequate accuracy. The findings provide insights into the underlying phenomena governing ion transport in IEMs to facilitate the rational development of more selective membranes.

Recovery of metal ion resources from waste lithium batteries by in situ electro-leaching coupled with electrochemically switched ion exchange.

A new green pathway of in situ electro-leaching coupled with electrochemically switched ion exchange (EL-ESIX) technology was developed for the separation and recovery of valuable metal ions from waste lithium batteries. By using the in situ electro-leaching, the leaching rates of Li+ and Co2+ from the prepared LiCoO2 film electrodes reached 100 % and 93.30 %, respectively, under the combined effect of the acidic microenvironment formed by the anodic electrolytic water and electrostatic repulsion. Subsequently, the Li+ in the electrolyte was further extracted by an electrochemically switched ion exchange (ESIX) process using LiMn2O4 as the film electrode, and Li+ was further enriched in the eluate by a cyclic adsorption and desorption process. The results indicate that the in situ electro-leaching has significant advantages over powder leaching, and for the recycling of waste lithium batteries, the final lithium recovery rate reached 94.51 % by using this in situ EL-ESIX technology.

Elucidating uranium interactions with synthetic Na-P1 zeolite/Ca2+-substituted alginate composite granules through batch and spectroscopic studies: Emphasizing the significance of ion exchange and complexation.

Uranium, a key member of the actinides series, is radioactive and may cause severe environmental hazards once discharged into the water due to high toxicity. Removal of uranium via adsorption by applying tailored, functional adsorbents is at the forefront of tackling such pollution. Here, we report the optimized functionalization of the powder coal fly-ash (CFA) derived Na-P1 synthetic zeolite to the form of granules by employing the biodegradable polymer-calcium alginate (CA) and their application to remove aqueous U. The optimized synthesis showed that granules are formed at the CA concentration equals to 0.5 % wt., and that application of 1% wt. solution renders the most effective U scavengers. The maximum U adsorption capacity (qmax) increases significantly after CA modification from 44.48 mgU/g for native, powder Na-P1 zeolite to 62.53 mg U/g and 76.70 mg U/g for 0.5 % wt. and 1 % wt. CA respectively. The U adsorption follows the Radlich-Peterson isotherm model, being the highest at acidic pH (pHeq∼4). The U adsorption kinetics reveals swift U uptake, reaching equilibrium after 2h for 1 % ZACB and 3 h for 0.5 % wt. ZACB following the pseudo-second-order (PSO) kinetic model. SEM-EDXS investigation elucidates that adsorbed U occurs onto materials as an inhomogenous, well-dispersed, and micrometer-scale aggregate. Further, XPS and µ-XRF spectroscopies complementarily confirmed the hexavalent oxidation state of adsorbed U and its altered distribution on ZACBs with varying CA concentrations. U distribution was probed "in-situ" onto materials while correlations between the major elements (Al, Si, Ca, U) contributing to U scavenging were calculated and compared. Finally, a real-life coal mine wastewater (CMW) polluted by 238U and 228,226Ra was successfully purified, satisfying WHO guidelines after treatment using ZACBs. These findings offer new insights on successful yet optimized Na-P1 zeolite modification using biodegradable polymer (Ca2+-exchanged alginate) aimed at efficient U removal, displaying a near-zero environmental impact.

Ion exchange synthesis of copper-based hydroxyapatite for the catalytic degradation of phenol.

Hydroxyapatite (HAP) is a material renowned for its exceptional capabilities in adsorbing and exchanging heavy metal ions, making it a widely employed substance within the environmental domain. This study aims to present a novel material, namely copper-HAP (Cu-HAP), which was synthesized via an ion exchange method. The resulting material underwent comprehensive characterization using scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller (BET) analysis. Subsequently, based on the principle of the Fenton-like oxidation reaction, the material was used for the degradation of phenol. The outcomes of the investigation revealed that the optimal preparation conditions for the catalyst were achieved at a temperature of 40 °C, a pH value of 5, and a relative dosage of Cu-HAP at 100 mg/g. Under the reaction conditions of a catalyst dosage of 2 g/L, a 30% hydrogen peroxide concentration of 30 mM, a phenol concentration of 20 mg/L, a pH value of 6, a temperature of 40 °C, and the degradation rate of phenol impressively reached 98.12%. Furthermore, the degradation rate remained at 42.31% even after five consecutive cycles, indicating the promising potential of Cu-HAP in the treatment of recalcitrant organic compounds within this field.

Using selectivity to evaluate aqueous- and resin-phase denitrification during biological ion exchange.

An increased fertilizer application for agricultural purposes has resulted in increased nitrate (NO3-) levels in surface water and groundwater around the globe, highlighting demand for a low-maintenance NO3- treatment technology that can be applied to nonpoint sources. Ion exchange (IEX) is an effective NO3- treatment technology and research has shown that bioregeneration of NO3- laden resins has the potential to minimize operational requirements and brine waste production that often prevents IEX application for decentralized treatment. In this work, batch denitrification experiments were conducted using solutions with low IEX selectivity capable of supporting the growth of denitrifying bacteria, while minimizing NO3- desorption from resins, encouraging resin-phase denitrification. Although only 15% of NO3- was desorbed by the low selectivity solution, this initial desorption started a cycle in which desorbed NO3- was biologically transformed to NO2-, which further desorbed NO3- that could be biotransformed. Denitrification experiments resulted in a 43% conversion rate of initially adsorbed NO3-, but biotransformations stopped at NO2- due to pH limitations. The balance between adsorption equilibria and biotransformation observed in this work was used to propose a continuous-flow reactor configuration where gradual NO3- desorption might allow for complete denitrification in the short retention times used for IEX systems.

Optimization of the chemolithotrophic denitrification of ion exchange concentrate using hydrogen-based membrane biofilm reactors.

A H2-based membrane biofilm reactor (MBfR) was used to remove nitrate from a synthetic ion-exchange brine made up of 23.8 g L-1 NaCl. To aid the selection of the best nitrate management strategy, our research was based on the integrated analysis of ionic exchange and MBfR processes, including a detailed cost analysis. The nitrate removal flux was not affected if key nutrients were present in the feed solution including potassium and sodium bicarbonate. Operating pH was maintained between 7 and 8. By using a H2 pressure of 15 psi, a hydraulic retention time (HRT) of 4 h, and a surface loading rate of 13.6 ± 0.2 g N m-2 d-1, the average nitrate removal flux was 3.3 ± 0.6 g N m-2 d-1. At HRTs of up to 24 h, the system was able to maintain a removal flux of 1.6 ± 0.2 g N m-2 d-1. Microbial diversity analysis showed that the consortium was dominated by the genera Sulfurimonas and Marinobacter. The estimated cost for a 200 m3/h capacity, coupled ion exchange (IX) + MBfR treatment plant is 0.43 USD/m3. This is a sustainable and competitive alternative to an IX-only plant for the same flowrate. The proposed treatment option allows for brine recycling and reduces costs by 55% by avoiding brine disposal expenses.

The effect of calcium removal from skim milk by ion exchange on the properties of the ultrafiltration retentate.

New processes are needed to produce concentrated milk feedstocks with tailored calcium content, due to the direct link between calcium concentration and final product texture and functionality. Skim milk treatment with cation exchange resin 1% (w/v) or 2% (w/v) prior to ultrafiltration to a volumetric concentration factor (VCF) of 2.5 or 5 successfully decreased the calcium concentration by 20-30% and produced concentrates with solids content at ∼22-24 g 100 g-1 at a VCF of 5. Calcium reduction partially solubilized the casein micelles, increasing the concentration of soluble protein and individual caseins, leading to decreased turbidity but increased protein hydration and hydrophobicity. Decalcification (2% (w/v) resin treatment) reduced thermal stability, significantly decreasing the denaturation temperature of α-lactalbumin and ß-lactoglobulin in the milk by ∼3 °C and ∼1 °C respectively. Filtration was also altered, reducing permeation flux and the gel concentration and increased filtration time. When combined, calcium reduction and filtration altered functional properties including soluble calcium, soluble protein and sedimentable solids, with increased milk protein hydration also contributing to increased viscosity. This study provides a route to produce calcium-reduced milk concentrates with potential for use in retentate-based dairy products with tailored functionality.

Embedded Mo/Mn Atomic Regulation for Durable Acidity-Reinforced HZSM-5 Catalyst toward Energy-Efficient Amine Regeneration.

Metal-molecular sieve composites with high acidity are promising solid acid catalysts (SACs) for accelerating sluggish CO2 desorption processes and reducing the energy consumption of CO2 chemisorption systems. However, the production of such SACs through conventional approaches such as loading or ion-exchange methods often leads to uncontrolled and unstable metal distribution on the catalysts, which limits their pore structure regulation and catalytic performance. In this study, we demonstrated a feasible strategy for improving the durability, surface chemical activity, and pore structure of metal-doped HZSM-5 through bimetallic Mo/Mn modification. This strategy involves the immobilization of Mo-O-Mn species confined in an MFI structure by regulating MoO42- anions and Mn2+ cations. The embedded Mn/Mo species of low valence can strongly induce electron transfer and increase the density of compensatory H+ on the MoMn@H catalyst, thereby reducing the CO2 desorption temperature by 8.27 °C and energy consumption by 37% in comparison to a blank. The durability enhancement and activity regulation method used in this study is expected to advance the rational synthesis of metal-molecular sieve composites for energy-efficient CO2 capture using amine regeneration technology.

The significance of heterophasic ion exchange in active biomonitoring of heavy metal pollution of surface waters.

We have carried out studies to examine the possibility of using biosorbents: the epigeic mosses Pleurozium schreberi (Willd. ex Brid.) Mitt., and the epiphytic lichens Hypogymnia physodes (L.) Nyl. in active biomonitoring of heavy metal pollution of surface waters. The dried sea algae Palmaria palmata (L.) Weber & Mohr were used as the third biosorbent. The studies were conducted in the waters of the Turawa Reservoir, a dam reservoir with a significant level of eutrophication in south-western Poland. Incremental concentrations of Mn, Ni, Zn, Cu, Cd, and Pb were determined in the exposed samples. It was shown that a 2-h exposure period increases the concentration of some metals in the exposed samples, even by as much as several hundred percent. High increments of nickel concentrations in the algae Palmaria palmata (mean: 0.0040 mg/g, with the initial concentration of c0 < 0.0016 in the algae) were noted, with negligible increments in concentrations of this metal in mosses and lichens. In contrast, mosses and lichens accumulated relatively high amounts of Cd (mean: 0.0033 mg/g, c0 = 0.00043 mg/g) and Pb (mean: 0.0243 mg/g, c0 = 0.0103 mg/g), respectively.

Extreme Monovalent Ion Selectivity Via Capacitive Ion Exchange.

Capacitive deionization (CDI) is an emerging technology applied to brackish water desalination and ion selective separations. A typical CDI cell consists of two microporous carbon electrodes, where ions are stored in charged micropore via electrosorption into electric double layers. For typical feed waters containing mixtures of several cations and anions, some of which are polluting, models are needed to guide cell design for a target separation, given the complex electrosorption dynamics of each species. An emerging application for CDI is brackish water treatment for direct agricultural use, for which it is often important to selectively electrosorb monovalent Na+ cations over divalent Ca2+ and Mg2+ cations. Recently, it was demonstrated that utilizing constant-voltage CDI cell charging with sulfonated cathodes and short charging times enabled monovalent-selective separations. Here, we utilize a one-dimensional transient CDI model for a flow-through electrode CDI cell to elucidate the mechanisms enabling such separations. We report the discovery that an asymmetric CDI cell with a chemically functionalized cathode induces electric charges in the pristine anode at 0 V cell voltage, which has important implications for monovalent cation selectivity. Leveraging our mechanistic understanding, with our model we uncover a novel operational regime we term "capacitive ion exchange", where the concentration of one ion species increases while competing species concentration decreases. This regime enables resin-less exchange of monovalent cations for divalent cations, with chemical-free electrical regeneration.