Search Results (14)

This study investigates the behavior of phosphate ion transport through two structurally distinct anion-exchange membranes—AMV (homogeneous) and HC-A (heterogeneous)—in an electrodialysis system under both static and stirred conditions at varying pH levels. Chronopotentiometric and current–voltage analyses were used to investigate the influence of pH and hydrodynamics on ion transport. Under underlimiting (ohmic) conditions, the AMV membrane exhibited simultaneous transport of H₂PO₄⁻ and HPO₄²⁻ ions at neutral and mildly alkaline pH, while such behavior was not verified at acidic pH and in all cases for the HC-A membrane. Under overlimiting current conditions, AMV favored electroconvection at low pH and exhibited significant water dissociation at high pH, leading to local pH shifts and chemical equilibrium displacement at the membrane–solution interface. In contrast, the HC-A membrane operated predominantly under strong electroconvective regimes, regardless of the pH value, without evidence of water dissociation or equilibrium change phenomena. Stirring significantly impacted the electrochemical responses: it altered the chronopotentiogram profiles through the emergence of intense oscillations in membrane potential drop at overlimiting currents and modified the current–voltage behavior by increasing the limiting current density, reducing electrical resistance, and compressing the plateau region that separates ohmic and overlimiting regimes. Additionally, both membranes showed signs of NH₃ formation at the anodic-side interface under pH 7–8, associated with increased electrical resistance. These findings reveal distinct ionic transport characteristics and hydrodynamic sensitivities of the membranes, thus providing valuable insights for optimizing phosphate recovery via electrodialysis. Full article

A comparative study of the physicochemical properties of natural bentonite clays of Pogodayevo (Republic of Kazakhstan, mod. 1) and Dash-Salakhli (Republic of Azerbaijan, mod. 2) deposits and modification of the bentonite clay with polyhydroxocations of iron (III) and aluminium (III). The amount of bentonite in the concentration of iron (aluminum) was 5 mmol Me³⁺/g. It was established that the modification of natural bentonites using polyhydroxocations of iron (III) (mod. 1_Fe_5-c, mod. 2_Fe_5-c) and aluminum (III) (mod. 1_Al_5-c, mod. 2_Al_5-c) by the method of “co-precipitation” leads to a change in their chemical composition, structural and sorption properties. The results showed that hydroxy-aluminum cations ([Al₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺) and poly-hydroxyl-Fe or polyoxo-Fe were intercalated into clay layers, which led to an increase in the values of d₀₀₁ and specific surface areas compared to those of the original bentonite, from 37 to 120 m²/g for the Pogodaevo bentonite and from 51 to 172 m²/g respectively, for bentonite from the Dash-Salakhli deposit. It is shown that modified sorbents based on natural bentonite are finely porous objects with a predominance of pores of 1.5–8.0 nm in size. As a result, there is a significant increase in the specific surface area of sorbents. Modification of bentonite with polyhydroxocations of iron (III) and aluminum (III) by the “co-precipitation” method also leads to an increase in the sorption capacity of the sorbents obtained with respect to nickel (II) cations. Modified bentonites were used for the adsorption of Ni (II) ions from the model solution. Ni (II) was absorbed in a neutral pH solution. The study of equilibrium adsorption showed that the data are in good agreement with the Langmuir isotherm model. The maximum adsorption capacity of the Ni (II) obtained from the Langmuir equation was 25.0 mg/g (mod. 1_Al_5-c), 18.2 mg/g (mod. 2_Al_5-c) for Al-bentonite and 16.7 mg/g (mod. 1_Fe_5-c), 10.1 (mod. 2_Fe_5-c) for Fe-bentonite. The kinetics of adsorption is considered. The high content of Al-OH anion exchange centers in them determines the higher sorption activity of Al-modified bentonites. Full article

In this study, phosphorus-doped watermelon rind carbon material (WC-M) was prepared by a muffle furnace, and the adsorption performance of WC-M material to dyes was investigated. At the same time, the effects of dye concentration, pH, adsorption time, adsorption temperature, and other factors on the adsorption effect were investigated. In the experiment, a muffle furnace was used to carbonize the watermelon rind doped with phosphoric acid, which simplified the experimental operation. Regarding the results of SEM analysis, the surface structure of WC-M materials is diverse. Isothermal maps of nitrogen adsorption and desorption show that the material contains more microporous structures and exhibits more active sites. The experimental results show that WC-M materials show good adsorption properties against cationic dyes (malachite green, MG) and anionic dyes (active black, AB). The neutral condition is conducive to the adsorption of MG, and the alkaline condition is conducive to the adsorption of AB. The adsorption rate reaches a maximum in the initial stage of adsorption, the adsorption capacity reaches 50% of the total adsorption capacity within 10 minutes before the reaction, and then the adsorption capacity gradually decreases until the adsorption equilibrium. The adsorption mechanism was explored by the pseudo-first-order kinetic model, second-order kinetic model, and intraparticle diffusion model. At the same time, through the analysis of multiple isotherm models, the overall adsorption process followed the Langmuir isotherm model, the adsorption of MG was more inclined to monolayer electron adsorption, and the adsorption capacity reached 182.68 mg⋅g⁻¹. The reusability of WC-M materials in MG and AB adsorption was discussed. At this time, the concentrations of AB and MG were 120 mg⋅L⁻¹ and 150 mg⋅L⁻¹, and after 10 h of desorption, the desorption rates of MG and AB reached 67.7% and 83.3%, respectively; after five adsorption–desorption cycles, the adsorption rate of MG was still 78.5%, indicating that WC-M materials have good recovery effect. At the same time, the use of watermelon rind as an adsorption material belongs to the high-value application of watermelon rind, which belongs to “turning waste into treasure” and will not pose a certain threat to the environment. This experiment is also suitable for durian rind, pineapple rind, and other “waste” biomass materials, and the experiment has certain generalizations. Full article

Co-sensitization of two or more light-absorbing compounds on a TiO₂ surface has recently become one of the most successful strategies in the development of dye-sensitized solar cells (DSSCs). The specific structure of the dyes for DSSCs implies that they can partly exist in anionic forms in popular solvents used for sensitization. Our study concerns the above two issues being analyzed in detail using the example of the popular carbazole (MK2) and indoline (D205) dyes, studied by stationary absorption and emission, femtosecond transient absorption (in complete cells and in the solutions), current-voltage measurements, DFT and TD-DFT theoretical calculations. After the addition of D205 to DSSC with MK2, the fill factor of the cells was improved, and the electron recombination between TiO₂ and the dyes was blocked (observed on sub-nanosecond time scales). Thus, the active co-adsorbent can take the role of the typically used passive additive, like chenodeoxycholic acid. Evidence of the concentration-dependent equilibrium between neutral and anionic forms of dyes with different lifetimes was found in acetonitrile solutions (the best for sensitization), while in ethanol solution the dominant form was the anion (worse for sensitization). Our findings should help in better understanding the operation and optimization of DSSC. Full article

Hydrothermally synthesized Linde type A (LTA) and faujasite X (FAU-X) zeolites are low-cost and environmentally benign inorganic carriers for environmental applications. In this study, (oxy)hydroxides were incorporated onto LTA and FAU-X zeolites to promote the phosphate adsorption. The performance of LTA-Fe and FAU-X-Fe was evaluated through batch adsorption assays. A complete evaluation was performed to recover phosphate from synthetic wastewater. The effect of pH, concentration, equilibrium, and kinetic parameters on phosphate adsorption and its further reuse in sorption–desorption cycles were evaluated. LTA-Fe and FAU-X-Fe are effective for adsorption of phosphate at neutral (e.g., pH 7.0 ± 0.2) and in a broad range of phosphate concentrations. Higher ratios of adsorption capacities were obtained by synthetic zeolites enriched with iron in comparison to their parent forms. The phosphate adsorption occurred through hydrogen bonding and complexation reactions between protonated iron hydroxyl groups and phosphate anions. The phosphate monolayer adsorption was followed by diffusion through the internal pores and 80% of the equilibrium adsorption was reached within 50 min. The LTA-Fe and FAU-X-Fe can be used for phosphate recovery from wastewater treatment plants. The use of LTA-Fe and FAU-X-Fe in a tertiary wastewater treatment stage could allow to reduce the phosphate–phosphorous content, reaching the regulatory levels (equal 1 mg L⁻¹ total phosphorous). The phosphate adsorption using LTA-Fe and FAU-X-Fe does not require pH adjustment, and it is endothermic. The reusability of both iron zeolites is limited, and they can be finally disposed for soil amendment applications. Full article

In recent years, there has been significant interest in the study of spandex in high-elasticity sensors. As a new kind of special spandex, dyeable spandex shows strong adsorption capacity for anions. In this study, neutral red G was used as an anion adsorption simulator to study the adsorption mechanism of dyeable spandex on anionic materials. The structure of dyeable spandex was characterized by the modern instrumental analysis method, and the adsorption kinetics and thermodynamics of neutral red G on dyeable spandex were discussed. The results show that the use of mixed amines as chain extenders for dyeable spandex reduced the regularity of molecules and the crystallinity of spandex, which was beneficial to the diffusion adsorption of anions. On the other hand, the number of secondary amino groups increased, providing more adsorption sites under acidic conditions. The adsorption of neutral red G on dyeable spandex satisfied the quasi-second-order kinetics and the Langmuir adsorption model, indicating that dye adsorption on spandex was mainly electrostatic. The diffusion coefficient and equilibrium adsorption capacity of neutral red G on dyeable spandex increased significantly, whereas enthalpy and entropy decreased. Full article

A nanocomposite based on graphene oxide and copper trimesinate was obtained by the in situ method. The samples have permanent porosity and a microporous structure with a large surface area corresponding to the adsorption type I. A study of the adsorption properties of the obtained composites with respect to organic dyes (malachite green, indigo carmine, brilliant green, Rose Bengal, crystal violet) showed that adsorption largely depends on the content of graphene oxide in the composites. The complex is an effective sorbent for the extraction of cationic and neutral organic dyes when the content of graphene oxide in the nanocomposite is 20% of the calculated copper trimesinate due to electrostatic forces of interaction. For anionic dyes, the maximum adsorption is achieved when using a composite containing 5% graphene oxide due to the predominance of physical sorption. Experimental results show that the obtained sorbent can be used for extraction in a wide pH range, illustrating the excellent pH window offered by this adsorbent. Kinetics data were properly fitted with the pseudo-second-order model. Equilibrium data were best correlated with the Freundlich model. The process was endothermic and spontaneous in nature. The composite makes it possible to achieve a maximum sorption of 393 mg/g, which is a sufficiently high value for the absorption of dyes. Full article

Karst water quality degradation has been a challenge for domestic and industrial water supplies worldwide. To reveal the possible factors response for karst water quality degradation, Baotu karst spring system is studied as an representative example. In this study, a hydrogeochemical investigation and mathematical, statistical, and geochemical modeling was conducted together to identify the major hydrochemical processes involved in the degradation process. It is found that the karst water is normally fresh, neutral-to-slightly alkaline, with calcium and magnesium as the predominant cations, and bicarbonate and sulfate as the predominant anions. The abnormally high chloride (95.05 mg/L) and nitrate concentrations (148.4 mg/L) give clues to the potential source of contamination in some karst water. The main hydrochemical facies of karst water are HCO₃-Ca and HCO₃ × SO₄-Ca, accounting for 76% of water samples. The water hydrochemistry is controlled mainly by the dissolution of carbonate minerals (calcite, dolomite), followed by the dissolution of silicate and gypsum. The dissolution of calcite and dolomite mostly happens in the recharge area. In the discharge area, the karst water is basically in equilibrium with calcite. The negative SI value of gypsum represents that the water–gypsum interaction is dominated by dissolution along the whole flow path. Cation exchange is observed in the karst water in the indirect recharge area. Along the flow path, the contents of chloride, sulfate, nitrate, and TDS (Total dissolved solids, abbreviated TDS, indicates how many milligrams of dissolved solids are dissolved in one liter of water) vary significantly, which is mostly affected by pollution from human industrial and agricultural activities. The concentrations of major ions were maintained at a low level (<20 mg/L) in the 1960s in karst water. The fast elevation of the parameter values has occurred in the past two decades. The temporal elevation of some pollutants in karst water suggest that global changes (acid rain) and human activity (such as overusing fertilizer) are main factors resulting in the degradation of karst water quality in the study area. The results of this paper provide invaluable information for the management and protection of karst water resources in the urban and rural areas. Full article

One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (^●OH) and azide (^●N₃) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ^●OH with 2-SeU are dominated by an absorption band with an λ_max = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2^●). The dimeric radical (2^●) is formed in the reaction of a selenyl-type radical (6^●) with 2-SeU, and both radicals are in equilibrium with K_eq = 1.3 × 10⁴ M⁻¹ at pH 4 (below the pK_a of 2-SeU). Similar equilibrium with K_eq = 4.4 × 10³ M⁻¹ was determined for pH 10 (above the pK_a of 2-SeU), which admittedly involves the same radical (6^●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2^●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λ_max = 390 nm, which was assigned to the ^●OH adduct to the double bond at C5 carbon atom (3^●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ^●N₃-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU. Full article

Intracellular transport of chloride by members of the CLC transporter family involves a coupled exchange between a Cl⁻ anion and a proton (H⁺), which makes the transport function dependent on ambient pH. Transport activity peaks at pH 4.5 and stalls at neutral pH. However, a structure of the WT protein at acidic pH is not available, making it difficult to assess the global conformational rearrangements that support a pH-dependent gating mechanism. To enable modeling of the CLC-ec1 dimer at acidic pH, we have applied molecular dynamics simulations (MD) featuring a new force field modification scheme—termed an Equilibrium constant pH approach (ECpH). The ECpH method utilizes linear interpolation between the force field parameters of protonated and deprotonated states of titratable residues to achieve a representation of pH-dependence in a narrow range of physiological pH values. Simulations of the CLC-ec1 dimer at neutral and acidic pH comparing ECpH-MD to canonical MD, in which the pH-dependent protonation is represented by a binary scheme, substantiates the better agreement of the conformational changes and the final model with experimental data from NMR, cross-link and AFM studies, and reveals structural elements that support the gate-opening at pH 4.5, including the key glutamates Glu_in and Glu_ex. Full article

Tris(2-methoxyethyl) fluoroborate anion (TMEFA), anovel tripodal ligand based on the BF₄⁻ superhalogen anion, is proposed and was investigated theoretically using ab initio MP2 (second-order Møller-Plesset perturbational method) and OVGF (outer valence Green function) methods. The studied molecule comprises three 2-methoxyethoxy groups (-O-CH₂-CH₂-O-CH₃) connected to a central boron atom, which results in the C₃-symmetry of the compound. The resulting anion was stable against fragmentation processes and its vertical electron detachment energy was found to be 5.72 eV. Due to its equilibrium structure resembling that of classical tripodal podands, the [F-B(O-CH₂-CH₂-O-CH₃)₃]⁻ anion is capable of binding metal cations using its three arms, and thus may form strongly bound ionic complexes such as [F-B(O-CH₂-CH₂-O-CH₃)₃]⁻/Li⁺ and [F-B(O-CH₂-CH₂-O-CH₃)₃]⁻/Mg²⁺. The binding energies predicted for such compounds far exceed those of the similar neutral classical podand ligands, which likely makes the [F-B(O-CH₂-CH₂-O-CH₃)₃]⁻ system a more effective molecular trap or steric shielding agent with respect to selected metal cations. Full article

Oxidative damage to 2-thiouracil (2-TU) by hydroxyl (^•OH) and azide (^●N₃) radicals produces various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by time-dependent density functional theory (TD-DFT) method. The transient absorption spectra recorded in the reactions of ^•OH with 2-TU depend on the concentration of 2-TU, however, only slightly on pH. At low concentrations, they are characterized by a broad absorption band with a weakly pronounced maxima located at λ = 325, 340 and 385 nm, whereas for high concentrations, they are dominated by an absorption band with λ_max ≈ 425 nm. Based on calculations using TD-DFT method, the transient absorption spectra at low concentration of 2-TU were assigned to the ^●OH-adducts to the double bond at C5 and C6 carbon atoms (3^●, 4^●) and 2c-3e bonded ^●OH adduct to sulfur atom (1…^●OH) and at high concentration of 2-TU also to the dimeric 2c-3e S-S-bonded radical in neutral form (2^●). The dimeric radical (2^●) is formed in the reaction of thiyl-type radical (6^●) with 2-TU and both radicals are in an equilibrium with K_eq = 4.2 × 10³ M⁻¹. Similar equilibrium (with K_eq = 4.3 × 10³ M⁻¹) was found for pH above the pK_a of 2-TU which involves admittedly the same radical (6^●) but with the dimeric 2c-3e S-S bonded radical in anionic form (2^●−). In turn, ^●N₃-induced oxidation of 2-TU occurs via radical cation with maximum spin location on the sulfur atom which subsequently undergoes deprotonation at N1 atom leading again to thiyl-type radical (6^●). This radical is a direct precursor of dimeric radical (2^●). Full article

Isothiazolones have been widely applied as non-oxidizing biocides to prevent biofouling of reverse osmosis (RO) membranes. However, few studies have investigated suitable RO concentrate treatments to remove these biocides. This study evaluated the adsorption behavior of four isothiazolone biocides, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 1,2-benzisothiazol-3(2H)-one (BIT), and 2-n-octyl-4-isothiazolin-3-one (OIT), by powdered activated carbon (PAC). Isothiazolones adsorption was found to obey pseudo second-order kinetics. Langmuir adsorption isotherms were more suitable to simulation of the adsorption effects than Freundlich isotherms. The adsorption amount followed the order OIT > BIT > CMIT > MIT, in accordance with the isothiazolones octanol/water partition coefficients (K_ow), indicating that hydrophobicity is the main factor for influencing adsorption amounts. Following normalization with K_ow, the amounts of isothiazolones adsorbed at equilibrium and normalized aqueous concentrations showed a linear relationship in a log-linear form. 1,2-benzisothiazol-3(2H)-one is anionic at high pH, and difficult to adsorb, while neutral BIT is more likely to be adsorbed. Textile reverse osmosis concentrate had an adverse effect on MIT, CMIT and BIT adsorption, but little effect on adsorption of OIT, which has a high log K_ow value. There was competition between organics and isothiazolones for PAC adsorption sites, which influenced the adsorption efficiency. Full article

Neutral starch microspheres (NSMs) were synthesized by an inverse microemulsion technology with epichlorohydrin as a crosslinker and soluble starch as starting material. Anionic starch microspheres (ASMs) were prepared from NSMs by the secondary polymerization with chloroacetic acid as the anionic etherifying agent. Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and laser diffraction particle size analyzer were used to characterize the anionic starch microspheres. The results showed that structure of the microspheres was compact and the hardness of microspheres was great, and the average diameter of the product was about 75 µm. The anionic starch microspheres (ASMs) were used to adsorb methylene blue (MB) from aqueous solution. Effects of adsorption time, initial concentration of MB, and temperature on the adsorption of MB onto ASMs were studied, and the equilibrium and kinetics of the adsorption process were further investigated. It shows that ASMs can effectively remove MB from the solution. The adsorption equilibrium data correlates well with the Langmuir isotherm model compared with Frendlich isotherem model. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model. Temperature variations did not significantly affect the adsorption of MB onto ASMs. Full article