Range Of Ionic Strengths Research Articles

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution – Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. The model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg2+. With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5–11), solute/solid ratio (1.37 × 10−5– 8.33 × 10−4 mol-solute/g-solid), ionic strengths (0.01 M – 0.7 M), and background electrolytes (Na+, Cs+, Rb+, Cl−, and NO3−) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg2+ to reduce Cd2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

Sol-gel transition diagram and theoretical study of κ-carrageenan in the presence of calcium ions

The gelation and melting temperatures of calcium-induced κ-carrageenan gels in the range of ionic strength 0–40 mmol/L were measured by small deformation oscillatory rheology. Theoretical studies of the interactions between dimeric unit models that form the κ-carrageenan polymer chain with Ca2+ cations were also carried out by means of quantum chemistry techniques using density functional theory with M06-2X/6-311G**. Gelling (on cooling) and melting (on heating) temperatures moved to progressively higher temperatures upon the progressive addition of CaCl2, yielding thermal hysteresis. The interactions of the κ-carrageenan model with Ca2+ ions were analyzed, and the results showed that κ-carrageenan can exhibit intra- and intermolecular hydrogen bonding and coordination with Ca2+ ions. The interaction energies that can present conformers of the κ-carrageenan model were located between 25.1 and 46.02 kJ/mol. Coordination between the Ca2+ cation and the polymer as well as the intra- and intermolecular interactions of two sugars may be one of the factors by which Ca2+ ions could promote the coil-helix transition, resulting in the formation of more aggregates acting as junction zones.

Empirical models to determine ions concentrations in lithium brines with high ionic strength

Argentina Puna brines are complex systems in which ions such as Na+, K+, Li+, Mg2+, Ca2+, SO42−, and B4O72− are presents. To obtain lithium carbonate from brines, they must be treated in order to increase its lithium concentrations and to eliminate the others ions that are presents in the brines. During concentration some salts can reach their solubility products (kps) and crystallize, producing different solid-liquid equilibriums. In order to design and select the process to purify the brine before lithium salts precipitation, it is necessary to know the other ions concentrations.Ion concentrations in solutions can be calculated based on the salts coefficient activities using Pitzer's model and its modifications. These methods have the restriction that can only be applied to solutions with ionic strength values up to 6 molal. The state of the art shows that the approach to study the equilibrium in complex system is to consider it as binary, ternary, quaternary and quinary systems. When ionic strength values are higher than 6 m the systems studied are binaries or have symmetrical ions.Brines of the Argentina Puna have, in general, initial ionic strength values around 6 molal and it increases when the brine is concentrated by evaporation, so the available thermodynamical models cannot be used to determine, beforehand, the final composition of a certain brine. In this work four different brines from four different Puna plateau in Argentina were evaporated to several degrees and ionic strength was calculated from the chemical brine's composition after each evaporation test. Ionic strength was found to correlate with the percentage of eliminated water following two different simple mathematical models, depending on the initial sulphate concentration of the brine and the possibility of its precipitation. Models to estimate the concentration of diluted ions of commercial value such as Li+, K+, and Mg2+ as function of ionic strength were also proposed. Ion concentrations could be modeled as function of the amount of eliminated water, once the correct relationship between this parameter and the ionic strength of the brine is established. These models correlate accurately ionic strength and ion concentrations for an ionic strength range from 4.8 to 15.4 molal; corresponding to percentages of water evaporated from 0% up to 60%.With these models it is possible to calculate beforehand the final ions concentrations after a given percentage of evaporated water. It allows to design brines processing and select the purification techniques without exhausting and time-consuming tests. Nowadays there are no tools that allows to do that, in consequence, each company must perform rigorous and numerous tests with its brines. Results of these work show that ionic strength is the parameter that unified brines behavior even if initial composition could be different. In consequence, it could be used as a parameter to describe brine behavior during evaporations.

Predicting Concentration- and Ionic-Strength-Dependent Air-Water Interfacial Partitioning Parameters of PFASs Using Quantitative Structure-Property Relationships (QSPRs).

Air-water interfacial retention of poly- and perfluoroalkyl substances (PFASs) is increasingly recognized as an important environmental process. Herein, column transport experiments were used to measure air-water interfacial partitioning values for several perfluoroalkyl ethers and for PFASs derived from aqueous film-forming foam, while batch experiments were used to determine equilibrium Kia data for compounds exhibiting evidence of rate-limited partitioning. Experimental results suggest a Freundlich isotherm best describes PFAS air-water partitioning at environmentally relevant concentrations (101-106 ng/L). A multiparameter regression analysis for Kia prediction was performed for the 15 PFASs for which equilibrium Kia values were determined, assessing 246 possible combinations of 8 physicochemical and system properties. Quantitative structure-property relationships (QSPRs) based on three to four parameters provided predictions of high accuracy without model overparameterization. Two QSPRs (R2 values of 0.92 and 0.83) were developed using an assumed average Freundlich n value of 0.65 and validated across a range of relevant concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and hexafluoropropylene oxide-dimer acid (i.e., GenX). A mass action model was further modified to account for the changing ionic strength on PFAS air-water interfacial sorption. The final result was two distinct QSPRs for estimating PFAS air-water interfacial partitioning across a range of aqueous concentrations and ionic strengths.

Climatic Chamber Stability Tests of Lipase-Catalytic Octyl-Sepharose Systems

The application of the climatic chamber presented in this paper to assess the storage stability of immobilized lipases is a new approach characterized by the potential of unifying the study conditions of biocatalysts created in various laboratories. The data achieved from storing lipases in the climatic chambers may be crucial for the chemical and pharmaceutical industry. Our paper describes the developed protocols for immobilization via interfacial activation of lipase B from Candida antarctica (CALB) and lipase OF from Candida rugosa (CRL-OF) on the Octyl-Sepharose CL-4B support. Optimization included buffers with different pH values of 4–9 and a wide range of ionic strength from 5 mM to 700 mM. It has been shown that the optimal medium for the CALB immobilization process on the tested support is a citrate buffer at pH 4 and high ionic strength of 500 mM. Implementing new optimal procedures enabled the hyperactivation of immobilized CALB (recovery activity 116.10 ± 1.70%) under the applicable reaction conditions using olive oil as a substrate. Importantly, CALB storage stability tests performed in a climatic chamber under drastic temperature and humidity conditions proved good stability of the developed biocatalyst (residual activity 218 ± 7.3% of dry form, after 7 days). At the same time, the low storage stability of CRL OF in a climatic chamber was demonstrated. It should be emphasized that the use of a climatic chamber to test the storage stability of a dry form of the studied lipases immobilized on Octyl-Sepharose CL-4B is, to our knowledge, described for the first time in the literature.

From speciation study to removal of Pb2+ from natural waters by a carnosine-based polyacrylamide/azlactone copolymer

A deep speciation study on L-carnosine (CAR) and Pb2+ system was performed in aqueous solution with the aim to assess its potential use as a sequestering agent of metal cation. To determine the best conditions for Pb2+ complexation, potentiometric measurements were carried out over a wide range of ionic strength (0.15 ≤ I/≤ 1 mol/L) and temperature (15 ≤ T/°C ≤ 37), and thermodynamic interaction parameters (logβ, ΔH, ΔG and TΔS) were determined. The speciation studies allowed us to simulate sequestration ability of CAR toward Pb2+ under different conditions of pH, ionic strength and temperature and to establish a priori the conditions for the best removal performance, i.e., pH > 7 and I = 001 mol/L. This preliminary investigation was very useful in optimizing removal procedures and limiting subsequent experimental measurements for adsorption tests. Therefore, to exploit the binding ability of CAR for Pb2+ removal from aqueous solutions, CAR was covalently grafted on an azlactone-activated beaded-polyacrylamide resin (AZ) using an efficient click coupling reaction (78.3% of coupling efficiency). The carnosine-based resin (AZCAR) was analyzed by ThermoGravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Differential Thermal Analysis (DTA). Morphology, surface area and pore size distribution were studied through a combination of Scanning Electron Microscope (SEM) and adsorption/desorption of N2 analyses according to the Brunauer-Emmett-Teller (BET) and Barret-Johner-Halenda (BJH) approaches. The adsorption capacity of AZCAR toward Pb2+ was investigated under conditions simulating the ionic strength and pH of different natural waters. The time needed to reach equilibrium in the adsorption process was 24 h, and the best performance was obtained at pH > 7, typical of most natural waters, with removal efficiency ranging from 90.8% (at I = 0.7 mol/L) to 99.0 (at I = 0.001 mol/L).

Redox-responsive degradable microgel modified with superparamagnetic nanoparticles exhibiting controlled, hyperthermia-enhanced drug release

A novel degradable microgel based on poly(N-isopropylacrylamide) (pNIPA) cross-linked with N,N’-bisacryloylcystine (BISS) and containing superparamagnetic iron oxide nanoparticles (SPION@CA) was synthesized by semi-batch precipitation polymerization and examined as a potential hyperthermia-enhanced drug carrier. The pNIPA provided the microgel with temperature sensitivity, the BISS was responsible for degradation in the presence of glutathione (GSH) (an –S–S–bond reductor naturally present in cells), while the SPION@CA permitted remote control of temperature to improve drug release. The microgels exhibited volume phase transition temperature at ca. 34 °C, which is near the human body temperature, and were stable across a wide range of temperatures and ionic strengths, as well as in the blood plasma at 37 °C. It was found that the presence of SPION@CA in the polymer network of the microgels enabled the temperature to be increased up to 42 °C by an alternating magnetic field, and that increasing the temperature from 37 to 42 °C significantly enhanced the releasing of the anticancer drug doxorubicin (DOX). The highest DOX release (82%) was observed at pH 5, 42 °C, and in the presence of GSH, and the lowest (20%) at pH 7.4, 37 °C, and in the absence of GSH. MTT assay indicated that compared to free doxorubicin, the microgel particles loaded with doxorubicin have comparable cytotoxicity against MCF-7 cancer cells while being significantly less toxic to MCF-10A healthy cells.Graphical abstract

Isotherm model discrimination for multimodal chromatography using mechanistic models derived from high-throughput batch isotherm data

In this work, we have examined an array of isotherm formalisms and characterized them based on their relative complexities and predictive abilities with multimodal chromatography. The set of isotherm models studied were all based on the stoichiometric displacement framework, with considerations for electrostatic interactions, hydrophobic interactions, and thermodynamic activities. Isotherm parameters for each model were first determined through twenty repeated fits to a set of mAb – Capto MMC batch isotherm data spanning a range of loading, ionic strength, and pH as well as a set of mAb – Capto Adhere batch data at constant pH. The batch isotherm data were used in two ways—spanning the full range of loading or consisting of only the high concentration data points. Predictive ability was defined through the model's capacity to capture prominent changes in salt gradient elution behavior with respect to pH for Capto MMC or unique elution patterns and yield losses with respect to gradient slope for Capto Adhere. In both cases, model performance was quantified using a scoring metric based on agreement in peak characteristics for column predictions and accuracy of fit for the batch data. These scores were evaluated for all twenty isotherm fits and their corresponding column predictions, thereby producing a statistical distribution of model performances. Model complexity (number of isotherm parameters) was then considered through use of the Akaike information criterion (AIC) calculated from the score distributions. While model performance for Capto MMC benefitted substantially from removal of low protein concentration data, this was not the case for Capto Adhere; this difference was likely due to the qualitatively different shapes of the isotherms between the two resins. Surprisingly, the top-performing (high accuracy with minimal number of parameters) isotherm model was the same for both resins. The extended steric mass action (SMA) isotherm (containing both protein-salt and protein-protein activity terms) accurately captured both the pH-dependent elution behavior for Capto MMC as well as loss in protein recovery with increasing gradient slope for Capto Adhere. In addition, this isotherm model achieved the highest median score in both resin systems, despite it lacking any explicit hydrophobic stoichiometric terms. The more complex isotherm models, which explicitly accounted for both electrostatic and hydrophobic interaction stoichiometries, were ill-suited for Capto MMC and had lower AIC model likelihoods for Capto Adhere due to their increased complexity. Interestingly, the ability of the extended SMA isotherm to predict the Capto Adhere results was largely due to the protein-salt activity coefficient, as determined via isotherm parameter sensitivity analyses. Further, parametric studies on this parameter demonstrated that it had a major impact on both binding affinity and elution behavior, therein fully capturing the impact of hydrophobic interactions. In summary, we were able to determine the isotherm formalisms most capable of consistently predicting a wide range of column behavior for both a multimodal cation-exchange and multimodal anion-exchange resin with high accuracy, while containing a minimized set of model parameters.

Missing Piece in Colloidal Stability─Morphological Factor of Hydrophobic Nanoparticles

Hydrophobic nanoparticles (NPs) in water were considered unstable because they lack the repulsive electrostatic interaction and steric effect to prevent aggregation. In this study, porous hydrophobic NPs of two star-shaped giant molecules, POSS-(R)8, were found to be stable in water and able to retain their kinetic stability in a wide range of temperatures, pH values, and ionic strengths. Unlike the solid hydrophobic NPs that aggregate even with the negative zeta potential (ζ) induced by surface-structured hydrogen-bonded (SHB) water, the porous morphology of POSS-(R)8 NPs reduces the entropically driven hydrophobic effect to prevent aggregation. With the porous morphology, the hydrophobic NPs are stable without the hydrophilic or charged surface functional groups and demonstrate good encapsulation capability. The morphological factor of colloids is thus one of the missing pieces in the theory of colloidal stability that extends our understanding of colloidal science.

Mechanisms of cardiac myosin replacement.

A recent mass spectrometry-based proteomic study from our lab demonstrated that newly synthesized myosin molecules are randomly inserted into preexisting thick filaments in adult mouse hearts in vivo. Therefore, we hypothesized that myosin molecules exist in a dynamic equilibrium between a filamentous pool required for contractility, and a monomeric pool required for myosin replacement. To test this hypothesis, we replaced 27 ± 7% of the cardiac myosin regulatory light chain (RLC) in adult mice with fluorescent RLC (GFP-RLC), via adeno-associated viral transfection. We visualized the random distribution of GFP-RLC within thick filaments in intact hearts with 2-photon microscopy, and the exchange of GFP-RLC between these filaments by quantifying fluorescence recovery after photobleaching (FRAP). Rapid FRAP occurred within minutes, when photobleaching small, ∼1-µm3 areas, of partial sarcomeres. These data demonstrate that the GFP-RLC exchanges between the thick filaments and a monomeric pool on a timescale that is orders of magnitude faster than that of protein replacement (t1/2 = 10.8 days). To determine whether the mechanism of this exchange may involve the folding of monomeric myosin, GFP-labeled myosin molecules were extracted from the transfected hearts and their Stokes radii were measured over a range of ionic strengths, using microfluidic diffusional sizing. At low ionic strengths (150 mM KCl), filament formation was favored, but the monomeric fraction of GFP-labeled myosin demonstrated a radius of 12.6±1.1 nm. At higher ionic strengths (400-600 mM KCl), the radius was increased to 18.0 nm. Similar radii have been reported for smooth muscle myosin monomers in folded and extended conformations. Together, these data suggest that myosin molecules exist in rapid equilibrium between a filamentous and monomeric pool within the sarcomere, and individual monomers may adopt a folded, compact conformation to regulate their exchange into, and out of filaments.

Supramolecular assembly of benzophenone alanine and copper presents high laccase-like activity for the degradation of phenolic pollutants.

Laccases are multicopper oxidases of significant importance for the degradation of phenolic pollutants. Because of the inherent defects of natural laccases in practical applications, herein, we discovered highly effective and non-cytotoxic laccase-like metallo-nanofibers based on the supramolecular assembly of single unnatural amino acid, benzophenone-alanine (BpA), in combination with copper ions. Structural analysis revealed that the catalytic BpA-Cu nanofibers possess a Cu(I)-Cu(II) electron transfer system similar to that in natural laccase. Our BpA-Cu nanofibers exhibit 4 times higher substrate affinity and 24% higher catalytic efficiency than the well-known high-performance industrialized laccase (Novozym 51003) in 2,4-dichlorophenol degradation. In addition, the BpA-Cu nanofibers were demonstrated to be stable (>75% residual activity) in long-term storage at a wide range of pH, ionic strength, temperature, ethanol, and water sample, and to be readily recovered for pollutant degradation, keeping 83% of the laccase activity after 10 catalytic recycles. Remarkably, the nanofibers displayed a wide substrate spectrum, detecting and degrading a variety of phenolic pollutants with high activity than other laccase mimics reported in the literature. Furthermore, the biocompatibility of the material was proved with cultured cells. These findings demonstrated the potential of BpA-Cu nanofibers in mimicking laccases for environmental remediation.

Coarse-grained intrinsically disordered protein simulations with explicit ions parameterized by salting-out constants.

Implicit solvent coarse-grained models have emerged as an effective method for simulating intrinsically disordered proteins (IDPs) due to the long length and time-scale need to effectively simulate their equilibrium behavior. These coarse-grained methods typically rely on Debye-Hückel theory to explain the effects of salt in the simulations. However, Debye-Hückel electrostatics are only accurate over a limited range of ionic strengths and are also unable to capture ion-type specific effects, typically called Hofmeister effects that arise at higher salt concentrations. To address this, we developed an explicit ion model of potassium chloride that can interface with the otherwise implicit solvent hydrophobicity scale model for intrinsically disordered protein. Parameters for the explicit ion model were determined by matching the salting-out constants of several small peptide-like molecules. Salting-out constants were determined in the simulation by creating a system with an ion concentration gradient via an external potential and performing umbrella sampling along the concentration gradient. The remaining amino acids for which there is no data for the salting-out constant are determined using a scaled Kapcha-Rosky hydrophobicity scale determined from the umbrella sampling simulations. The parameters are validated against a set FRET data from a diverse set of linker peptides at several salt concentrations. This explicit ion model is able to capture the changes in protein expansion as a function of salt concentration at concentration above 0.5 M where Debye-Hückel screened electrostatics predict no change in protein expansion.

Activity Coefficients of the System {yKCl + (1 – y)KH2PO4}(aq) at T = 298.15 K Determined by Cell Potential Measurements

Zero-current cell potential measurements were used to determine the solution activity coefficient in a ternary system {yKCl + (1 – y) KH2PO4}(aq) at temperature T = 298.15 K. The cell of the type K–ISE|KCl(mKCl), KH2PO4(mKH2PO4)|Ag|AgCl was used in the total ionic strength range, Im = 0.0886–1.0046 mol kg–1. In order to generate a set of parameters that can be applied in a wide range of mixed solution ionic strengths, the Pitzer, Scatchard, and Clegg–Pitzer–Brimblecombe models were used to fit all available experimental data, including cell potential and isopiestic measurements from the literature. The experimental and calculated values of thermodynamic properties for the studied system are in excellent agreement. Potential interactions and solution structure were discussed by means of the excess free energy of mixing via potential pairs, triplets, or quads for the investigated solution using the Scatchard model mixing parameters.

A fundamental model for calculating interfacial adsorption of complex ionic and nonionic PFAS mixtures in the presence of mixed salts.

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants that have been used extensively as firefighting agents and in a wide range of commercial applications around the world. As many of the most-common PFAS components are surfactants, they readily accumulate at interfaces, a process that can govern their environmental fate. There are thousands of PFAS compounds, and they have nearly always been used as mixtures, so it is common to find many different PFAS components present together in the environment. Furthermore, the interfacial behavior of ionic PFAS can be strongly influenced by the presence of salts, with adsorption dependent on both the composition and concentration of salts present. Any predictions of PFAS interfacial behavior made without considering both the mixed nature of PFAS present, as well as the composition of the salts present, have the potential to be off by orders of magnitude. To date, models capable of making predictions of PFAS interfacial adsorption when both mixed PFAS and mixed salts are present have not been presented. The work described here addresses this need by extending a mass-action model developed previously by the authors to allow predictions in cases where complex combinations of mixed PFAS and mixed salts are present. Predictions of PFAS interfacial affinity for a range of PFAS mixture conditions and ionic strengths are verified using experimentally-measured surface tension data. The new model provides physically-realistic prediction of interfacial adsorption of a wide range of PFAS mixtures over a wide range of salt concentrations and compositions. The model is capable of predicting interfacial adsorption of ionic/nonionic PFAS mixtures in the presence of salts, and can also make predictions when there is competitive adsorption between different PFAS components, a common case in PFAS source zones where high concentrations of multiple components are present and in foam fractionation reactors.

Benzoylthiourea based polymers as new binding agents for diffusive gradients in thin films technique in labile mercury determination in freshwaters

In this study, the diffusive gradient in thin film (DGT) has been developed using three new materials derived from benzoylthiourea (PBTU, BTP1 and BTP2) for the determination of bioavailable mercury (Hg). The efficiency of these DGT devices was compared with the well-established 3-mercaptopropyl functionalized silica gel (3MFS) in laboratory and field conditions. It was found that PBTU lacked of consistency for handling and assembling in the DGT device, whereas the other two polymers provided mechanically stable binding gels and extracted satisfactorily Hg. However, BTP2 showed no correlation between Hg uptake and Hg present in the aqueous solution, and therefore, BTP1 gels was chosen as the binding layer used for DGT technique. The calculated diffusion coefficient of DGT-BTP1 was 4.0 × 10 −6 cm 2 s −1 at 25 °C in 0.8 mm thick diffusion layer and 2.3% w/v of material in gel, whereas for DGT-3MFS, the D value was 9.1 × 10 −6 cm 2 s −1 . Moreover, it was found that neither the pH (range 4.5 – 9.5) nor the ionic strength (range 0.005–0.1 mol L −1 ) significantly affected the binding behavior of Hg (p > 0.05). Finally, the DGT-BTP1 devices were successfully used for in-situ measurements of Hg in Quito River (Colombia), impacted by artisanal gold mining, and were compared with DGT-3MFS. Results showed a good performance with values of the labile Hg concentration between 5 to 8% of the total Hg in water. This study demonstrates that benzoylthiourea based DGT is a useful tool for in situ monitoring of Hg in freshwaters. • Three new materials derived from benzoylthiourea were used for DGT technique. • BTP1 extracted satisfactorily Hg, with a diffusion coefficient of 4.0 × 10 −6 cm 2 s −1 . • DGT-BTP1 was suitable for aqueous solutions with a wide pH and ionic strength range. • These devices were successfully used in a Colombian river highly impacted by Hg. • Benzoylthiourea based DGT was a useful tool for in situ monitoring of Hg in freshwaters.

Cellulose nanofiber from pomelo spongy tissue as a novel particle stabilizer for Pickering emulsion

For the high-value utilization of agricultural wastes to promote sustainable development, in this work, pomelo spongy tissue cellulose nanofibers (PCNFs) with lengths >3 μm and widths 33–64 nm were prepared by high pressure homogenization (HPH). The PCNFs were used to stabilized Pickering emulsion, and the emulsion with oil phase fraction in the range of 10 % to 50 % (w/w) exhibited outstanding stability. The increase in PCNFs concentration also enhanced the three-dimensional network structure, resulting in higher stability of the emulsion. Moreover, the droplet size distribution of emulsion would be greatly improved by moderate heating. No creaming was observed in emulsions over a wide range of ionic strengths (20–200 mM) after storage for 30 d. And the excellent emulsifying properties of the PCNFs were mainly attributed to their adsorption at the oil-water interface and the formation of a three-dimensional network structure. All the results indicated that the PCNF would be a promising novel stabilizer for Pickering emulsions.

Preparation of starch-acrylic acid-carboxymethyl cellulose copolymer and its flocculation performance towards methylene blue

Flocculants synthesized from biopolymers show the virtues of low cost, excellent efficiency and environmental friendliness. In this study, starch-acrylic acid-carboxymethyl cellulose (SAC) tertiary anionic copolymers were prepared by graft copolymerization. The optimal synthesis process was determined as raw material ratio of 1:3:1, acrylic acid neutralization degree of 70%, initiator dosage of 1.0 wt%, reaction temperature of 75 °C and reaction time of 5 h according to the flocculation performance towards methylene blue simulated waste water. Results demonstrated that the decolorization ratio of methylene blue (100 mg/L) could be up to 81.3% at the SAC dosage of 350 mg/L. The SAC achieved rapid flocculation kinetics and excellent color removal over a broad range of pH, ambient temperature and ionic strength. Furthermore, the operation cost of SAC is only one-fourth of industrial anionic polyacrylamide. The prepared SAC flocculant is promising for industrial dye wastewater treatment owing to its green raw materials, high efficiency and low operation cost.

Key factors in the adsorption of natural organic matter to metal (hydr)oxides: Fractionation and conformational change

Adsorption of natural organic matter (NOM) to mineral surfaces is an important process determining the environmental fate and biogeochemical cycling of many elements. Natural organic matter consists of a heterogeneous mixture of soft and flexible organic molecules. Upon adsorption, size fractionation may occur, as well as changes in molecular conformation. Although very important, these phenomena have been omitted in existing adsorption models. Filling this gap, a novel framework for NOM adsorption to metal (hydr)oxides is presented. Humic acid (HA) was used as an analog for studying experimentally the NOM adsorption to goethite and its size fractionation as a function of pH, ionic strength, and surface loading. Size fractionation was evaluated for adsorption isotherms collected at pH 4 and 6, showing HA molecules of low molar mass were preferentially adsorbed. This phenomenon was incorporated into the new model. Consistent description of the HA adsorption data over the entire range of pH (3–11), ionic strength (2–100 mM), and surface loading (0.1–3 mg m−2) indicated that the spatial distribution of HA molecules adsorbed in the interface is a trade-off between maximizing the interaction of the HA ligands with the oxide surface and minimizing the electrostatic repulsion between HA particles as a result of interfacial crowding. Our advanced consistent framework is able to quantify changes in molar mass and molecular conformation, thereby significantly contributing to an improved understanding of the competitive power of HA for interacting on oxides with other adsorbed small organic acids as well as environmentally important oxyanions, such as phosphate, arsenate, and others.

Environmental behaviour of a pesticide metabolite, the AMPA. Sequestration of Ca2+, Mg2+, Cu2+, Zn2+ and Al3+

The chelating and sequestering ability of a glyphosate metabolite, the aminomethylphosphonic acid (AMPA) towards bi- and trivalent metal cations, such as Ca2+, Mg2+, Zn2+, Cu2+ and Al3+, were investigated in aqueous solutions of NaCl, in an ionic strength range of 0.1 ≤ I/mol dm−3 ≤ 1.0 and at constant temperature of T = 298.15 ± 0.15 K. The investigations on the acid-base properties and complexing ability were performed, by means of potentiometry, in conditions of different cM:cAMPA molar ratios and pH values. The formation of insoluble species was experimentally observed in the Mn+/AMPA2− systems, and the solid phases were characterized by means of X-Ray Diffractometry (XRD), Scanning Electron Microscopy (SEM) and InfraRed Attenuated Total Reflection spectroscopy (IR-ATR). The dependence on ionic strength of the stability constants of the Mn+/AMPA2− complexes species, determined at different ionic strengths, was modelled by the Debye-Hückel type equation. The sequestering ability of AMPA toward the investigated metal cations was evaluated by pL0.5 parameter.

Improving in vivo Uranyl Removal Efficacy of a Nano‐Metal Organic Framework by Interior Functionalization with 3‐Hydroxy‐2‐pyridinone

Comprehensive SummaryThe environmental contamination of uranium will occur in scenarios such as nuclear accidents and leakage from nuclear waste storage sites, which eventually leads to the internal uranium exposure of people, causing consequential injuries of renal failure, osteosarcoma, etc. The development of uranyl specific chelating agents that could sequester uranium in vivo is in urgent need and is important for the safe and efficient development of nuclear industry. Metal organic frameworks (MOFs) already serve as efficient uranium depletion materials in solutions of a wide range of pH and ionic strength for nuclear fuel recycling, uranium extraction from seawater, as well as environmental decontamination. Herein, a chromium‐based nano‐metal organic framework (nano‐MOF) functionalized interiorly with 3,2‐HOPO ligands, MIL‐101‐HOPO, is rationally synthesized. In vitro adsorption experiments show that MIL‐101‐HOPO exhibits high adsorption selectivity and fast adsorption kinetics for uranyl. The results of in vivo uranyl decorporation assays reveal that MIL‐101‐HOPO with the decoration of HOPO ligands on the interior wall exhibits significantly increased uranyl removal ratio in kidneys comparing to the pristine nMOFs, and is more effective than the clinically used ZnNa3‐DTPA. All those results corroborate the interior functionalization of MOFs as an efficient strategy to develop promising uranyl decorporation agents.