Multivalent Cations Research Articles

Silk sericin-coated polyamide thin-film composite membranes to simultaneously improve anti-scaling properties, long-term storage, and waste-to-resource recovery

A polyamide thin-film composite (PA-TFC) membrane, which is one of the widely used for desalination and water softening processes, features a lot of carboxyl groups inevitably formed by hydrolysis of unreacted acyl chlorides after interfacial polymerization. However, since carboxyl groups interact with multivalent cations and thereby cause membrane scaling, it is desirable to reduce the density of carboxyl groups on the membrane surface. In this regard, silk sericin (SS) can be an excellent alternative to modifying the surface characteristics to mitigate scaling because it has various hydrophilic amino acids with a much lower density of carboxyl groups per unit mass. Given the properties, we prepared anti-scaling TFC membranes by coating SS on the PA active layer. According to the result, the SS-PA-TFC (16.4% decrease) significantly reduced the flux decline to half of the PA-TFC (36.7% decrease) during the 48-h scaling test under the condition for heterogeneous gypsum crystal nucleation. More importantly, the comparison of operation duration until cleaning obviously revealed the anti-scaling properties of the SS-PA-TFC, which was evidenced by about 7.5 times longer duration than the PA-TFC. Furthermore, the cyclic scaling test in 19 mM CaSO4 showed that the SS-PA-TFC (3.6%) could decrease the irreversible fouling to about one-fifth of the PA-TFC (15.9%). This outstanding anti-scaling performance of the SS-PA-TFC stemmed from the less negatively charged (‐40.8 and ‐28.1 mV for the PA-TFC and SS-PA-TFC, respectively) and much more hydrophilic surface (52.2° and 18.2° for the contact angles of the PA-TFC and SS-PA-TFC, respectively). Suprisingly, the above-mentioned anti-scaling properties of the SS-PA-TFC membrane were achieved without the trade-off between water flux and salt rejection thanks to a very thin SS coating layer (ca. 16 nm). Apart from the anti-scaling properties, SS coating also improved long-term storage and waste-to-resource recovery.

Facile sol–gel synthesis of trivalent Al3+-Gd3+ ions co-doped nanoscale cobalt spinel ferrite for magneto-electronic applications

The magnetic spinel ferrites nanomaterials simultaneously doped with multivalent cations have gained a lot of interest from many researchers during the last decade. Also, the doping of trivalent rare-earth ions in spinel ferrites is promising for many technological applications. Considering these facts, in this work we investigated the trivalent Al3+-Gd3+ ions co-doped cobalt ferrite nanoparticles with nominal composition as CoFe2-2xAlxGdxO4 (x = 0.00, 0.03, 0.05, 0.07, 0.10). The sol–gel auto ignition route assisted by citric acid as a chelating agent was utilized to synthesize the series of nanoparticles. The Rietveld refined X-ray diffraction (XRD) patterns were analyzed to ensure the single-phase formation of nanoparticles with spinel cubic structure. The spherical-shaped grain morphology of the nanoparticles was indicated by scanning electron microscopy (SEM) images. The elemental analysis obtained by energy dispersive X-ray analysis (EDAX) revealed stoichiometric formation of the samples along with high purity. The two prominent frequency modes analogous to the spinel ferrite structure were noted in the infrared spectra assuring the successful formation of all the samples. The soft magnetic behaviour with a lower coercivity of the prepared nanoparticles was confirmed by the vibrating sample magnetometer (VSM) technique. The DC electrical resistivity plots indicated that resistivity decreases with an increase in Al3+-Gd3+ co-doping. The dielectric studies of all the samples showed increasing behaviour with an increase in Al3+-Gd3+ co-doping. All the results suggest that the Al3+-Gd3+ co-doped cobalt ferrite nanoparticles can be useful for real-world applications, specifically in nanoelectronics devices.

Tailor-Made Heterocharged Covalent Organic Framework Membrane for Efficient Ion Separation.

Pore size sieving, Donnan exclusion, and their combined effects seriously affect ion separation of membrane processes. However, traditional polymer-based membranes face some challenges in precisely controlling both charge distribution and pore size on the membrane surface, which hinders the ion separation performance, such as heavy metal ion removal. Herein, the heterocharged covalent organic framework (COF) membrane is reported by assembling two kinds of ionic COF nanosheets with opposite charges and different pore sizes. By manipulating the stacking quantity and sequence of two kinds of nanosheets, the impact of membrane surface charge and pore size on the separation performance of monovalent and multivalent ions is investigated. For the separation of anions, the effect of pore size sieving is dominant, while for the separation of cations, the effect of Donnan exclusion is dominant. The heterocharged TpEBr/TpPa-SO3H membrane with a positively charged upper layer and a negatively charged bottom layer exhibits excellent rejection of multivalent anions and cations (Ni2+, Cd2+, Cr2+, CrO4 2-, SeO3 2-, etc). The strategy provides not only high-performance COF membranes for ion separation but also an inspiration for the engineering of heterocharged membranes.

The role of glycerol in manufacturing freeze-dried chitosan and cellulose foams for mechanically stable scaffolds in skin tissue engineering

Various strategies have extensively explored enhancing the physical and biological properties of chitosan and cellulose scaffolds for skin tissue engineering. This study presents a straightforward method involving the addition of glycerol into highly porous structures of two polysaccharide complexes: chitosan/carboxymethyl cellulose (Chit/CMC) and chitosan/oxidized cellulose (Chit/OC); during a one-step freeze-drying process. Adding glycerol, especially to Chit/CMC, significantly increased stability, prevented degradation, and improved mechanical strength by nearly 50%. Importantly, after 21 days of incubation in enzymatic medium Chit/CMC scaffold has almost completely decomposed, while foams reinforced with glycerol exhibited only 40% mass loss. It is possible due to differences in multivalent cations and polymer chain contraction, resulting in varied hydrogen bonding and, consequently, distinct physicochemical outcomes. Additionally, the scaffolds with glycerol improved the cellular activities resulting in over 40% higher proliferation of fibroblast after 21 days of incubation. It was achieved by imparting water resistance to the highly absorbent material and aiding in achieving a balance between hydrophilic and hydrophobic properties. This study clearly indicates the possible elimination of additional crosslinkers and multiple fabrication steps that can reduce the cost of scaffold production for skin tissue engineering applications while tailoring mechanical strength and degradation.

Experimental Investigation on the Interfacial Characteristics of Tight Oil Rocks Induced by Tuning Brine Chemistry.

Currently, research on enhancing imbibition oil recovery in tight oil reservoirs through the ion-tuning technique remains limited. Two critical parameters for capillary imbibition are the wettability and interfacial tension between oil and water. In this investigation, we manipulate the properties of two types of formation water for both aged and unaged samples by diluting brine and altering ion composition. Subsequently, we employ captive and pendant-drop methods to assess rock wettability and interfacial tension under varied brine conditions. Additionally, we elucidate the primary mechanisms underlying changes in rock wettability and interfacial tension. Meanwhile, we analyze capillarity characteristics and assess the relative significance of wettability and interfacial tension. Results indicate that there is a critical interfacial tension with progressive dilution of two types of formation water. However, modifying ion composition leads to a complex trend in interfacial tension, which can be explained qualitatively through the Gibbs adsorption isotherm. For unaged samples, the contact angle demonstrates a pronounced water-wet characteristic, showing a nonmonotonic trend with respect to dilution times. Remarkably, the rock surface exhibits the strongest water-wet, particularly evident in the case of FW-10, largely influenced by variations in interfacial tension. Conversely, aged samples demonstrate strong oil-wet, with a critical salinity resulting in the lowest contact angle, while altering brine ion types can alter rock wettability from strongly oil-wet to intermediate-wet, which is not sufficient to result in the wettability alteration. The removal of multivalent cations is proposed as the most effective method for wettability modification. Furthermore, capillarity variations among different brine cases are primarily contingent upon contact angle changes, and interfacial tension does not have a significant change when regulating the brine properties. Consequently, we emphasize the significance of wettability in the adoption of ion-tuned brine techniques for tight oil reservoirs. Overall, our study underscores the potential of reasonably regulating brine properties to enhance capillarity and, thereby, improve imbibition oil recovery.

Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries

The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. In this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV2O4) spinel cathode during the Mg2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI-) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.

An Organic-Inorganic Hydrogel with Exceptional Mechanical Properties via Anion-Induced Synergistic Toughening for Accelerating Osteogenic Differentiation.

Mineralized bio-tissues achieve exceptional mechanical properties through the assembly of rigid inorganic minerals and soft organic matrices, providing abundant inspiration for synthetic materials. Hydrogels, serving as an ideal candidate to mimic the organic matrix in bio-tissues, can be strengthened by the direct introduction of minerals. However, this enhancement often comes at the expense of toughness due to interfacial mismatch. This study reveals that extreme toughening of hydrogels can be realized through simultaneous in situ mineralization and salting-out, without the need for special chemical modification or additional reinforcements. The key to this strategy lies in harnessing the kosmotropic and precipitation behavior of specific anions as they penetrate a hydrogel system containing both anion-sensitive polymers and multivalent cations. The resulting mineralized hydrogels demonstrate significant improvements in fracture stress, fracture energy, and fatigue threshold due to a multiscale energy dissipation mechanism, with optimal values reaching 12MPa, 49kJm-2, and 2.98kJm-2. This simple strategy also proves to be generalizable to other anions, resulting in tough hydrogels with osteoconductivity for promoting in vitro mineralization of human adipose-derived mesenchymal stem cells. This work introduces a universal route to toughen hydrogels without compromising other parameters, holding promise for biological applications demanding integrated mechanical properties.

Modulating ion coordination environment for improved Li+/Mg2+ selectivity in mixed solutions

AbstractThe outstanding ionic sieving capabilities of the nanoporous membranes have been evident; however, the selectivity in mixed solutions is often lower than that in single salt solutions. Given that the inherent properties of nanochannels remain the same, the ionic coordination structure in mixed solution becomes a remarkable factor for the inferior selectivity, and may change due to the interaction between anions and multivalent cations, a phenomenon rarely explored. Herein, molecular simulations demonstrated some free hydrated ions transfer to ionic clusters consisting of multi‐ions in representative LiCl/MgCl2 mixed solutions, and the ionic permeability discrepancy is exponentially associated with ionic cluster change. Ionic clusters are engaged by the enhanced coordination of chloride ions under the interference of divalent cations. Hence, by introducing anions with weak coordination ability, this detrimental effect is mitigated and ion selectivity is improved. This work provides essential theoretical foundations for further ion sieving applications in complex system.

Quantitative study on the metal dissolution reaction with multivalent cations by a modified SECM mode: Pure Ti as a case

Metal corrosion exhibits coupled multi-reaction features, making it challenging to quantitatively study the dissolution reaction with variable-valent cations, particularly in valence quantification. This work develops a novel scanning electrochemical microscopy mode and applies it to Ti dissolution study in acidic fluorides. This mode identifies the potential-dependent corrosion reactions and quantifies the valence evolution of Ti from HER to transpassive regions. Results provide direct electrochemical evidence for soluble Ti(z≤3), for the first time, and revise the reported dissolution equation. The proposed mode overcomes the drawbacks of macro-electrochemical analysis based on coupling information and provides an effective quantitation method for anodic reactions.

Cation-induced morphological transitions and aggregation of thermoresponsive PNIPAM nanogels

Poly(N-isopropylacrylamide) (PNIPAM) nanogels are promising responsive colloidal particles that can be used in pharmaceutical applications as drug carriers. This work investigates the temperature-dependent morphological changes and agglomeration of PNIPAM nanogels in the presence of mono- and multi-valent cationic electrolytes. We described the deswelling, flocculation, thermal reversibility behaviour and aggregated morphology of PNIPAM nanogels over a range of electrolyte concentrations and temperatures revealing the critical transition points from stable suspension to spontaneous agglomeration. We demonstrated that the flocculating ability and the rate of aggregate formation follow the order of deswelling behaviour. Transmission electron microscopy and atomic force microscopy analysis revealed the presence of a shell-like layer with varying density in the multivalent electrolyte solutions when compared to those in aqueous medium. We identified a concentration threshold of the thermally induced reversible aggregation/dispersion for the PNIPAM nanogels in the presence of Na+ and K+ ions at 10 mM, for Mg2+ and Ca2+ ions at 1 mM and for Al3+ ions at 0.1 mM concentrations. Such concentration thresholds indicated the effective destabilization of the electrolyte system with multivalency following the Schulze–Hardy rule. Our findings were supported by applying a Debye screening model that accounts for the shielding effect of multivalent cationic electrolytes on these nanogel systems. Our experiments and the models confirmed the compression of the electric double layer as the valency and ionic strength increased, except for Al3+ at higher concentrations which seemed to disrupt the electrical double layer and cause reversal of zeta potential. Our work highlights the significant impact the presence of multivalent cations can impose on the stability and morphology of nanogels, and this understanding will help in designing responsive nanogel systems based on PNIPAM nanogels.

A Unified Charge Storage Mechanism to Rationalize the Electrochemical Behavior of Quinone-Based Organic Electrodes in Aqueous Rechargeable Batteries.

Due to their eco-sustainability and versatility, organic electrodes are promising candidates for large-scale energy storage in rechargeable aqueous batteries. This is notably the case of aqueous hybrid batteries that pair the low voltage of a zinc anode with the high voltage of a quinone-based (or analogue of quinone-based) organic cathode. However, the mechanisms governing their charge-discharge cycles remain poorly understood and are even a matter of debate and controversy. No consensus exists on the charge carrier in mild aqueous electrolytes, especially when working in an electrolyte containing a multivalent metal cation such as Zn2+. In this study, we comprehensively investigate the electrochemical reactivity of two model quinones, chloranil, and duroquinone, either diluted in solution or incorporated into carbon-based composite electrodes. We demonstrate that a common nine-member square scheme proton-coupled electron transfer mechanism allows us to fully describe and rationalize their electrochemical behavior in relation to the pH and chemical composition of the aqueous electrolyte. Additionally, we highlight the crucial role played by the pKas associated with the reduced states of quinones in determining the nature of the charge carrier that compensates for the negative charges reversibly injected in the active material. Finally, contrary to the widely reported findings for Zn/organic batteries, we unequivocally establish that the predominant solid-state charge carriers in Zn2+-based mild aqueous electrolytes are not multivalent Zn2+ cations but rather protons supplied by the weakly acidic hexaaqua metal ions (i.e., [Zn(H2O)6]2+]).

Tautomeric pillars in vanadyl phosphate cathode to screen the divalent charge on Zn2+ for aqueous Zn batteries

Cathode materials with high redox potential are important for constructing high-energy-density aqueous zinc batteries. The polyanion compound of layered hydrate vanadyl phosphate (H2O-VOP) provides high potential thanks to the inductive effect. However, the sluggish Zn2+ diffusion in the lattice results in large voltage hysteresis, obstructing the capacity release at high voltage. Herein, tautomeric pillars are inserted in the VOPO4 layers (Tau-VOP) by the desulfhydryl reaction of l-cysteine, aiming to suppress voltage hysteresis with their charge screening effect. Specifically, the Lewis alkaline sites on the tautomers capture inserted Zn2+, and the divalent charge is further delocalized over the conjugated structure of pillars. This reduction of effective charge on cations ensures much weakened electrostatic interactions with the lattice and reduced diffusion barrier. As a result, the Tau-VOP cathode achieves 193 mAh g−1 capacity with 1.47 V/1.6 V redox voltage in zinc cells, which are superior to 110 mAh g−1 capacity and 1.1 V average discharge voltage with large voltage hysteresis obtained with H2O-VOP. The rate performance and energy efficiency are also significantly improved with the help of tautomer pillars. This work presents an effective charge screening strategy by suitable pillars to facilitate multivalent cation transport in cathode structures and enhance electrochemical performance.

Influence of Zr-doping on the structure and transport properties of rare earth high-entropy oxides

Fluorite-type ceria-based ceramics are well established as oxygen ion conductors due to their high conductivity, superseding state-of-the-art electrolytes such as yttria-stabilized zirconia. However, at a specific temperature and oxygen partial pressure they occasionally exhibit electronic conduction attributed to polaron hopping via multivalent cations (e.g. Pr and Ce). (Ce, La, Pr, Sm, Y)O2−δ is a high-entropy oxide with a fluorite-type structure, featuring low concentrations of multivalent cations that could potentially mitigate polaron hopping. However, (Ce, La, Pr, Sm, Y)O2−δ undergoes a structural transition to the bixbyite-type structure above 1000 °C. In this study, we introduce Zr doping into (Ce, La, Pr, Sm, Y)O2−δ to hinder the structural transition at elevated temperatures. Indeed, the fluorite structure at elevated temperatures is stabilized at approximately 10 at.% Zr doping. The total conductivity initially increases with doping, peaking at 5 at.% Zr doping, and subsequently decreases with further doping. Interestingly, electronic conductivity in (Ce, La, Pr, Sm, Y)1−x Zr x O2−δ under oxidizing atmospheres is not significant and is lowest at 8 at.% Zr. These results suggest that ceria-based high-entropy oxides can serve as oxygen ion conductors with a significantly reduced electronic contribution. This work paves the way for new compositionally complex electrolytes as well as protective coatings for solid oxide fuel cells.

Improved Mechanical Strength without Sacrificing Li-Ion Transport in Polymer Electrolytes.

Next-generation batteries demand solid polymer electrolytes (SPEs) with rapid ion transport and robust mechanical properties. However, many SPEs with liquid-like Li+ transport mechanisms suffer a fundamental trade-off between conductivity and strength. Dynamic polymer networks can improve bulk mechanics with minimal impact to segmental relaxation or ionic conductivity. This study demonstrates a system where a single polymer-bound ligand simultaneously dissociates Li+ and forms long-lived Ni2+ networks. The polymer comprises an ethylene oxide backbone and imidazole (Im) ligands, blended with Li+ and Ni2+ salts. Ni2+-Im dynamic cross-links result in the formation of a rubbery plateau resulting in, consequently, storage modulus improvement by a factor of 133× with the introduction of Ni2+ at rNi = 0.08, from 0.014 to 1.907 MPa. Even with Ni2+ loading, the high Li+ conductivity of 3.7 × 10-6 S/cm is retained at 90 °C. This work demonstrates that decoupling of ion transport and bulk mechanics can be readily achieved by the addition of multivalent metal cations to polymers with chelating ligands.

Developing energy-efficient nitrate-to-ammonia flow cells with bifunctional NiFeW-oxide thin-film electrodes made by magnetron sputtering technique

Herein, we develop a sputtered NiFeW-oxide thin-film bifunctional electrocatalyst with the incorporated oxygen vacancies and multivalent cations of Ni2+/3+, Fe2+/3+, and W6+ to enhance the economic viability of electrocatalytic nitrate reduction for commercial applications. Our NFW-0.5 achieves a notable 54.6 mg/h.cm2 ammonia yield rate at a modest applied potential of −0.2 V vs. RHE, coupled with an outstanding Faradaic efficiency of 93.7%. Furthermore, our NFW-0.5(+)‖NFW-0.5(−) flow-cell electrolyzer with a larger electrode of 2×2 cm2 reveals an impressive ammonia productivity of 143.5 mg/h.cm2 at a cell voltage of 2.0 V, accompanied by a superior Faradaic efficiency of 96.1%, an energy efficiency of 26%, and a low energy consumption of 26.3 kWh/kg.NH3. An oxygen vacancy-based NO3-pinned mechanism is proposed to explain our excellent nitrate reduction. Our work introduces a new paradigm to design efficient and bifunctional electrocatalysts for potential industrial-scale ammonia production.

Multivalent-Ion versus Proton Insertion into Nanostructured Electrochromic WO3 from Mild Aqueous Electrolytes.

Mild aqueous electrolytes containing multivalent metal salts are currently scrutinized for the development of ecosustainable energy-related devices. However, the role of soluble multivalent metal ions in the electrochemical reactivity of transition metal oxides is a matter of debate, especially when they are performed in protic aqueous electrolytes. Here, we have compared, by means of (spectro)electrochemistry, the reversible electrochromic reduction of transparent nanostructured γ-WO3 thin films in mild aqueous electrolytes of various chemical composition and pH. This study reveals that reversible proton insertion is the only charge storage mechanism over a large pH range and that it is effective for aqueous electrolytes prepared from either organic (such as acetic acid) or inorganic (such as solvated multivalent cations) Bro̷nsted acids. By refuting charge storage mechanisms relying on the reversible insertion of multivalent metal ions, notably in aqueous electrolytes based on Al3+ ions or a mixture of Al3+ and Zn2+ ions, these fundamental results pave the way for the rational development of electrolytes and active materials for a range of aqueous-based devices, such as the emerging concept of an energy-saving smart window, which we also address in this study.

Potential Co2+ and Ni2+ intercalation into nickel hexacyanoferrate in aqueous media: Study of electrochemical process and multivalent batteries implications

Alternative energy storage systems to lithium-ion batteries that can reduce the dependency on such technology have attracted great interest in recent years. Besides their current limitations, multivalent batteries based on coupling a metallic anode (Mg, Zn, Ca…) with a multivalent intercalation cathode are considered as a potential option. Prussian Blue Analogues (PBAs) have shown promising multivalent intercalation capacities and have also been employed in other scientific fields like wastewater treatment, selective element extraction, and may have a potential applicability in batteries recycling. However, some controversies have recently appeared around the capacity of PBAs to incorporate multivalent cations in aqueous media. In this work, we analyze by a combinatorial approach using structural and electrochemical techniques the potential Ni2+ and Co2+ intercalation in K0.61Ni[Fe(CN)6]0.84□0.16·2·12H2O, its limitations, the role of proton intercalation and the cation released after oxidation, which differed from the intercalated during previous reduction step. The potential implications of such findings in current uses of PBAs for multivalent batteries are also discussed.

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI)2 and Mg(TFSI)2.

Silicon is drawing attention as an emerging anode material for the next generation of lithium-ion batteries due to its higher capacity compared with commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components, creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer are mitigated by utilizing a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of the silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in situ fashion and a more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage in comparison to that of the baseline electrolyte due to reduced side reactions. Electron microscopy, HR-XRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface, and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing the bulk and forming a more stable SEI in comparison to baseline electrolyte and electrolyte with single multivalent cations.

Heavy Metal Removal from Aqueous Solutions Using a Customized Bipolar Membrane Electrodialysis Process.

Lack of safe water availability and access to clean water cause a higher risk of infectious diseases and other diseases as well. Heavy metals (HMs) are inorganic pollutants that cause severe threats to humans, animals, and the environment. Therefore, an effective HM removal technology is urgently needed. In the present study, a customized bipolar membrane electrodialysis process was used to remove HMs from aqueous solutions. The impacts of the feed ionic strength, applied electrical potential, and the type and concentration of HMs (Cd2+, Co2+, Cr3+, Cu2+, and Ni2+) on the process performance were investigated. The results showed that feed solution pH changes occurred in four stages: it first decreased linearly before stabilizing in the acidic pH range, followed by an increase and stabilization in the basic range of the pH scale. HM speciation in the basic pH range revealed the presence of anionic HM species. The presence of HMs on anion exchange membranes confirmed the contribution of these membranes for HM removal in the base channels of the process. While no clear trend was seen in the ionic strength solution, the maximum HM removal was observed when 1.5 g/L NaCl was used. The initial HM concentration showed a linear increase in HMs removal of up to 30 mg/L. A similar trend was seen with an increase in the applied electrical potential of up to 15 V. In general, the amount of HMs removed increased in the following order: Cd2+ ˃ Ni2+ ˃ Co2+ ˃ Cu2+ ˃ Cr3+. Under some operational conditions, however, the removed amount of Cu2+, Co2+, and Ni2+ was similar. The mass balance and SEM-EDX results revealed that the removed HMs were sorbed onto the membranes. In conclusion, this process efficiently separates HMs from aqueous solutions. It showed the features of diluate pH adjustment, reduction in the overall stack electrical resistance, and contribution of anion exchange membranes in multivalent cation removal. The mechanisms involved in HMs removal were diffusion and migration from the bulk solution, followed by their sorption on both cation and anion exchange membranes.

Assessing groundwater quality dynamics in Madhya Pradesh: Chemical contaminants and their temporal patterns

Groundwater is essential for maintaining ecosystem health and overall well-being as a pivotal resource for plants and animals. The increasing public consciousness of the deterioration of groundwater quality has emphasized the significance of undertaking extended evaluations of groundwater water quality, particularly in regions undergoing substantial hydrological alterations. This study primarily aims to investigate the spatio-temporal variations in groundwater quality and evaluate its suitability for potable purposes in the region of Madhya Pradesh. The study combines the Mann-Kendall (MK) test and Sen's Slope (SS) to analyze the changes in groundwater quality of all 51 districts of Madhya Pradesh, India, utilizing 12 water quality indices using MATLAB. Data was sourced from the Central Ground Water Board (CGWB) in India from the year 2001–2021. The data was then tested for homogeneity at all 1154 sampling stations using the software XLSTAT. Piper plot clustering characterized the state's groundwater as bicarbonate-calcium-magnesium (HCO3−-Ca2+-Mg2+) type. The study found that the groundwater in the area is heavily impacted by high levels of nitrate and hardness, which is caused by an increase in multivalent cations. The water was classified as ranging from hard to extremely hard, and approximately 25.49% of the state's groundwater has nitrate levels that exceed the acceptable limits. The MK test showed a significant increasing correlation in trends for parameters such as nitrate, sulfate, fluoride, chloride, bicarbonate, total hardness, and electrical conductivity. It also showed a significant decreasing correlation for calcium, magnesium, potassium, and sodium. These results were observed at a confidence level of 95%. The analysis of trends has shown that human-related factors have a considerable effect on the characteristics of groundwater quality. It is therefore recommended that such human-related factors be taken into consideration when developing policies for managing groundwater resources. Consequently, these policies should emphasize the strict enforcement of rules and standards that limit the overuse of fertilizers, ensure the appropriate disposal of municipal solid and liquid wastes, and regulate industrial pollutants.