Raman spectroscopy investigation and improved knowledge on industrial cation-exchange membranes involved in electrodialysis process

NASA Astrophysics Data System (ADS)

Chaouki, M.; Huguet, P.; Bribes, J.-L.

1996-06-01

Raman spectra of three specific, industrial, cation-exchange membranes (CEMs) have shown the existence of an extra vibrational band. The relative intensity of this band is different in each membrane spectrum recorded. Chlorosulfonation of polymeric ethylenetrifluoroethylene (ETFE) film grafted with polystyrene chains is used to obtain these CEMs involved in the electrodialysis process. A Raman study of the above reaction has been undertaken and has shown that non-sulfonated polystyrene rings give rise to this extra vibrational band. Different behavior of CEMs synthesized under similar conditions can be explained by a variable amount of non-sulfonated polystyrene rings contained in these materials.

Simultaneous determination of cations, zwitterions and neutral compounds using mixed-mode reversed-phase and cation-exchange high-performance liquid chromatography.

PubMed

Li, Jingyi; Shao, Shan; Jaworsky, Markian S; Kurtulik, Paul T

2008-03-28

A novel mixed-mode reversed-phase and cation-exchange high-performance liquid chromatography (HPLC) method is described to simultaneously determine four related impurities of cations, zwitterions and neutral compounds in developmental Drug A. The commercial column is Primesep 200 containing hydrophobic alkyl chains with embedded acidic groups in H(+) form on a silica support. The mobile phase variables of acid additives, contents of acetonitrile and concentrations of potassium chloride have been thoroughly investigated to optimize the separation. The retention factors as a function of the concentrations of potassium chloride and the percentages of acetonitrile in the mobile phases are investigated to get an insight into the retention and separation mechanisms of each related impurity and Drug A. Furthermore, the elution orders of the related impurities and Drug A in an ion-pair chromatography (IPC) are compared to those in the mixed-mode HPLC to further understand the chromatographic retention behaviors of each related impurity and Drug A. The study found that the positively charged Degradant 1, Degradant 2 and Drug A were retained by both ion-exchange and reversed-phase partitioning mechanisms. RI2, a small ionic compound, was primarily retained by ion-exchange. RI4, a neutral compound, was retained through reversed-phase partitioning without ion-exchange. Moreover, the method performance characteristics of selectivity, sensitivity and accuracy have been demonstrated to be suitable to determine the related impurities in the capsules of Drug A.

Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption.

PubMed

Fukushi, Keisuke; Sakai, Haruka; Itono, Taeko; Tamura, Akihiro; Arai, Shoji

2014-09-16

Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs(+) desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca(2+) and Mg(2+) (>0.5 mM) and high concentrations of K(+). The order of ability for Cs desorption was Na(+) = K(+) > Ca(2+) = Mg(2+) at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs(+) desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments.

Process and apparatus for the production of BI-213 cations

DOEpatents

Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

1998-01-01

A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

Process and apparatus for the production of Bi-213 cations

DOEpatents

Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

1998-12-29

A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

Characterization of new polymer-grafted protein cation exchangers developed by partial neutralization of carboxyl groups derivatized by modification of poly(ethylenimine)-Sepharose with succinic anhydride.

PubMed

Zhao, Yangyang; Dong, Xiaoyan; Yu, Linling; Liu, Yang; Sun, Yan

2018-05-18

Previously, we have studied protein adsorption and chromatographic behaviors on poly(ethylenimine) (PEI)-grafted Sepharose FF anion-exchange resins, and found that protein uptake rates increased greatly when PEI grafting density reached over a critical ionic capacity (cIC) due to the occurrence of the "chain delivery" effect. Moreover, by partial charge neutralization of starting resin FF-PEI-L740 (IC = 740 mmol/L, larger than the cIC) with sodium acetate to FF-PEI-R440, it exhibited a three-fold increase in uptake rate over FF-PEI-L740. In this work, to take the advantages of PEI and extend the applications of the PEI-grafted resins in cation-exchange chromatography, a series of cation exchangers of five different ICs were developed. First, the charged of FF-PEI-L740 was reversed from positive to negative by reaction with excess succinic anhydride, which created a cation-exchanger with an IC of 970 mmol/L (FF-FEI-C970). FF-PEI-C970 was further modified with ethanolamine for partial charge neutralizations, leading to the preparation of four charge-reduced cation exchangers with IC values (in mmol/L) of 780, 630, 560 and 430, which were denoted as FF-PEI-CR780, -CR630 -CR560 and -CR430, respectively. Protein adsorption and chromatographic behaviors were investigated using lysozyme (Lys) as the model protein. It was found that, the resins of high and moderate IC values (IC ≥ 560 mmol/L) afforded adsorption capacities up to over 230 mg/mL. Besides, the uptake rate, represented by the effective pore diffusivity (D e/ D 0 ), exhibited significant increase from 0.067 (FF-PEI-C970 and FF-PEI-CR780) to 0.343 (FF-PEI-CR630 and FF-PEI-CR560) and then to 1.035 (FF-PEI-CR430) with decreasing IC. It was considered that decreasing IC led to the decreased protein binding sites (binding strength), which encouraged the occurrence of the "chain delivery" effect. Moreover, the resins of high and moderate IC values, particularly, the resins of moderate IC values (FF-PEI-CR630 and FF-PEI-CR560), presented both high adsorption capacities and uptake kinetics at 0-100 mmol/L NaCl. Besides, dynamic binding capacity achieved 150 mg/mL for the resins of moderate IC values at 0 mmol/L NaCl concentration, and afforded >110 mg/mL for the resin of high IC values at 0-100 mmol/L NaCl concentration. The results proved the excellent IEC performance of the PEI-derived cation exchangers. Copyright © 2018 Elsevier B.V. All rights reserved.

The dynamical behavior of the s-trioxane radical cation-A low-temperature EPR and theoretical study.

PubMed

Naumov, Sergej S; Knolle, Wolfgang; Naumov, Sergej P; Pöppl, Andreas; Janovský, Igor

2014-10-28

The radical cation of s-trioxane, radiolytically generated in a freon (CF3CCl3) matrix, was studied in the 10-140 K temperature region. Reversible changes of the EPR spectra were observed, arising from both ring puckering and ring inversion through the molecular plane. The ESREXN program based on the Liouville density matrix equation, allowing the treatment of dynamical exchange, has been used to analyze the experimental results. Two limiting conformer structures of the s-trioxane radical cation were taken into account, namely "rigid" half-boat and averaged planar ones, differing strongly in their electron distribution. The spectrum due to the "rigid" half-boat conformer can be observed only at very low (<60 K) temperatures, when the exchange of conformers is very slow. Two transition states for interconversion by puckering and ring-inversion were identified, close in activation energy (2.3 and 3.0 kJ/mol calculated). Since the energy difference is very small, both processes set on at a comparable temperature. In the case of nearly complete equilibration (fast exchange) between six energetically equivalent structures at T > 120 K in CF3CCl3, a septet due to six equivalent protons (hfs splitting constant 5.9 mT) is observed, characteristic of the dynamically averaged planar geometry of the radical cation. DFT quantum chemical calculations and spectral simulation including intramolecular dynamical exchange support the interpretation.

Selective Gas Capture Ability of Gas-Adsorbent-Incorporated Cellulose Nanofiber Films.

PubMed

Shah, Kinjal J; Imae, Toyoko

2016-05-09

The 2,2,6,6-tetramethylpiperidine-1-oxyl radical-oxidized cellulose nanofibers (TOCNF) were hybridized with cation and anion-exchange organoclays, where poly(amido amine) dendrimers were loaded to enhance the functionality of gas adsorption, since dendrimers have the high adsorbability and the enough selectivity on the gas adsorption. The thin films were prepared from the organoclay-TOCNF hybrids and supplied to the gas adsorption. The adsorption of CO2 and NH3 gases increased with an increasing amount of organoclays in TOCNF films, but the behavior of the increase depended on gases, clays, and dendrimers. The hydrotalcite organoclay-TOCNF films displayed the highest adsorption of both gases, but the desorption of CO2 gas from hydrotalcite organoclay-TOCNF films was drastically high in comparison with the other systems. While the CO2 gas is adsorbed and remained on cationic dendrimer sites in cation-exchange organoclay-TOCNF films, the CO2 gas is adsorbed on cationic clay sites in anion exchange organoclay-TOCNF films, and it is easily desorbed from the films. The NH3 adsorption is inversive to the CO2 adsorption. Then the CO2 molecules adsorbed on the cationic dendrimers and the NH3 molecules adsorbed on the anionic dendrimers are preferably captured in these adsorbents. The present research incorporated dendrimers will be contributing to the development of gas-specialized adsorbents, which are selectively storable only in particular gases.

High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

PubMed

Rey, M A

2001-06-22

One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands

PubMed Central

Fan, Zhaochuan; Lin, Li-Chiang; Buijs, Wim; Vlugt, Thijs J. H.; van Huis, Marijn A.

2016-01-01

Cation exchange is a powerful tool for the synthesis of nanostructures such as core–shell nanocrystals, however, the underlying mechanism is poorly understood. Interactions of cations with ligands and solvent molecules are systematically ignored in simulations. Here, we introduce the concept of pseudoligands to incorporate cation-ligand-solvent interactions in molecular dynamics. This leads to excellent agreement with experimental data on cation exchange of PbS nanocrystals, whereby Pb ions are partially replaced by Cd ions from solution. The temperature and the ligand-type control the exchange rate and equilibrium composition of cations in the nanocrystal. Our simulations reveal that Pb ions are kicked out by exchanged Cd interstitials and migrate through interstitial sites, aided by local relaxations at core–shell interfaces and point defects. We also predict that high-pressure conditions facilitate strongly enhanced cation exchange reactions at elevated temperatures. Our approach is easily extendable to other semiconductor compounds and to other families of nanocrystals. PMID:27160371

Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

PubMed

Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

2013-11-19

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors.

PubMed

Li, Shixiang; Zhang, Xulan; Bei, Er; Yue, Huihui; Lin, Pengfei; Wang, Jun; Zhang, Xiaojian; Chen, Chao

2017-08-01

N-nitrosodimethylamine (NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine (DMA) and ranitidine (RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal (DMA>78% and RNTD>94%) observed at pHMg 2+ >RNTD + >K + >DMA + >NH 4 + >Na + . The partition coefficient of DMA + to Na + was 1.41±0.26, while that of RNTD + to Na + was 12.1±1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca 2+ were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes. Copyright © 2017. Published by Elsevier B.V.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

PubMed

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of dissymmetric cationic gemini surfactants at silica/water interface

NASA Astrophysics Data System (ADS)

Sun, Yuhai; Feng, Yujun; Dong, Hongwei; Chen, Zhi

2007-05-01

Adsorption of a series of cationic gemini surfactants 12-2- m ( m = 8, 12, 16) on the surface of silica was investigated. The critical micelle concentrations, cmcs, of cationic gemini surfactants in the initial solutions and in the supernatants were measured by conductometry and tensiometer. The changes in cmc values indicate that the ion exchanges take place between polar groups of gemini surfactants adsorbed and ions bound on the surface of silica. The adsorption isotherms of cationic gemini surfactants were obtained by a solution depletion method. Based on the driving force, the adsorption includes two steps, one of which is ion exchange, and the other is hydrophobic interaction. In each step, the tendency of surfactant molecules in the solution to form aggregates or to be adsorbed on the silica varies with their structures. The maximum adsorption amount of gemini surfactants on the silica, τmax, decreases as increasing in the length of one alkyl chain, m, from 8, 12 to 16. So the results show that the adsorption behaviors of gemini surfactants are closely related to the dissymmetry of gemini molecules.

High-performance cation-exchange chromatofocusing of proteins.

PubMed

Kang, Xuezhen; Frey, Douglas D

2003-03-28

Chromatofocusing using high-performance cation-exchange column packings, as opposed to the more commonly used anion-exchange column packings, is investigated with regard to the performance achieved and the range of applications possible. Linear or convex gradients in the range from pH 2.6 to 9 were formed using a variety of commercially available column packings that provide a buffering capacity in different pH ranges, and either polyampholytes or simple mixtures having a small number (three or fewer) of buffering species as the elution buffer. The resolutions achieved using cation-exchange or anion-exchange chromatofocusing were in general comparable, although for certain pairs of proteins better resolution could be achieved using one type of packing as compared to the other, evidently due to the way electrostatic charges are distributed on the protein surface. Several chromatofocusing methods were investigated that take advantage of the acid-base properties of commercially available cation-exchange column packings. These include the use of gradients with a composite shape, the use of very low pH ranges, and the use of elution buffers containing a single buffering species. The advantages of chromatofocusing over ion-exchange chromatography using a salt gradient at constant pH were illustrated by employing the former method and a cation-exchange column packing to separate beta-lactoglobulins A and B, which is a separation reported to be impossible using the latter method and a cation-exchange column packing. Trends in the apparent isoelectric points determined using cation- and anion-exchange chromatofocusing were interpreted using applicable theories. Results of this study indicate that cation-exchange chromatofocusing is a useful technique which is complementary to anion-exchange chromatofocusing and isoelectric focusing for separating proteins at both the analytical and preparative scales.

Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases.

PubMed

Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

2012-07-01

The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous process of preparation of n-butyl(meth)acrylate by esterification of (meth)acrylic acid by butanol on thermostable sulfo-cation exchanger

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheleznaya, L.L.; Karakhanov, R.A.; Lunin, A.F.

1987-11-10

The authors propose an effective thermostable sulfo-cation exchanger based on polymers with a system of conjugated bonds, sulfopolyphenylene ketone (SPP) differing from the known cation exchangers by the high thermostability (up to 250/sup 0/C), and also having the effect of the stabilization of the double bond in unsaturated monomers. The combination of inhibiting and cation exchange properties makes it also possible to use these sulfo-cation exchangers in the processes of esterification of (meth)acrylic acids by alcohols without addition of special inhibitors. The SPP catalyst was tested in esterification processes of acrylic an methacrylic acid by butanol at a pilot plant.

Production of sodium-22 from proton irradiated aluminum

DOEpatents

Taylor, Wayne A.; Heaton, Richard C.; Jamriska, David J.

1996-01-01

A process for selective separation of sodium-22 from a proton irradiated minum target including dissolving a proton irradiated aluminum target in hydrochloric acid to form a first solution including aluminum ions and sodium ions, separating a portion of the aluminum ions from the first solution by crystallization of an aluminum salt, contacting the remaining first solution with an anion exchange resin whereby ions selected from the group consisting of iron and copper are selectively absorbed by the anion exchange resin while aluminum ions and sodium ions remain in solution, contacting the solution with an cation exchange resin whereby aluminum ions and sodium ions are adsorbed by the cation exchange resin, and, contacting the cation exchange resin with an acid solution capable of selectively separating the adsorbed sodium ions from the cation exchange resin while aluminum ions remain adsorbed on the cation exchange resin is disclosed.

Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

PubMed Central

2013-01-01

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

Impacts of Pantoea agglomerans strain and cation-modified clay minerals on the adsorption and biodegradation of phenanthrene.

PubMed

Tao, Kelin; Zhao, Song; Gao, Pin; Wang, Lijin; Jia, Hanzhong

2018-06-06

Interactions between microorganisms and minerals have the potential contribution to remove polycyclic aromatic hydrocarbons (PAHs) in model systems. In this study, phenanthrene (PHE) was used as a probe molecule to explore the potential adsorption and biotransformation processes in the presence of microorganisms and various reference clays, such as montmorillonite (M), kaolinite (K), and pyrophyllite (P). Equilibrium adsorption experiments and scanning electron microscopy (SEM) technique were used to investigate the sorption of Pantoea agglomerans strains on clay minerals saturated with cations (Na + and Fe 3+ ). The adsorption isotherms of PHE and Pantoea agglomerans strains on cation-modified clay minerals fitted to Langmuir equation, and their adsorbed amounts both followed the sequence: montmorillonite > kaolinite > pyrophyllite. For six types of cation-modified minerals, the behavior of PHE adsorbed and Pantoea agglomerans adhered onto mentioned minerals was in the order of Na(I)-M > Fe(Ⅲ)-M, Na(I)-K > Fe(Ⅲ)-K and Fe(Ⅲ)-P > Na(I)-P, respectively. The biodegradation results showed that cation-modified clay minerals could enhance the biodegradation of PHE, ascribing to their large specific surface area, and cation exchange capability, as well as the difference in zeta potential between minerals and Pantoea agglomerans strains. Comparison of biodegradation rates displayed that PHE was degraded the highest in the presence of Na-M (93.285%). In addition, the obtained results suggested that the adhesion of bacteria onto cation-exchanged clay minerals was beneficial to the biodegradation of PHE. Anthracen-9-ylmethanol and 3,4-dimethyl-2-(3-methylbutanoyl)benzoic acid were detected as the main intermediate compounds, which can be further biodegraded into small molecules. The overall results obtained in this study are of valuable significance for the understanding of the behavior of PHE in soil and associated environment. Copyright © 2018 Elsevier Inc. All rights reserved.

Development of a stable cation modified graphene oxide membrane for water treatment

NASA Astrophysics Data System (ADS)

Yu, Wenzheng; (Yet Yu, Tong; Graham, Nigel

2017-12-01

Membranes prepared from layers of graphene oxide (GO) offer substantial advantages over conventional materials for water treatment (e.g. greater flux), but the stability of GO membranes in water has not been achieved until now. In this study the behavior of GO membranes prepared with different quantities and species of cations has been investigated to establish the feasibility of their application in water treatment. A range of cation-modified GO membranes were prepared and exposed to aqueous solutions containing specific chemical constituents. In pure water, unmodified and Na-modified GO membranes were highly unstable, while GO membranes modified with multivalent cations were stable provided there were sufficient quantities of cations present; their relative capability to achieve GO stability was as follows: Al3+  >  Ca2+  >  Mg2+  >  Na+. It is believed that the mechanism of cross-linking, and membrane stability, is via metal-carboxylate chelates and cation-graphite surface interactions (cation-π interaction), and that the latter appears to increase with increasing cation valency. The instability of cation (Ca or Al)-modified GO membranes by NaCl solutions during permeation occurred as Na+ exchanged with the incorporated multivalent cations, but a high content of Al3+ in the GO membrane impeded Al3+/Na+ exchange and thus retained membrane stability. In solutions containing biopolymers representative of surface waters or seawater (protein and polysaccharide solutions), Ca-GO membranes (even with high Ca2+ content) were not stable, while Al-GO membranes were stable if the Al3+ content was sufficiently high; Al-formed membranes also had a greater flux than Ca-GO membranes.

Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays

USGS Publications Warehouse

Chiou, Cary T.; Rutherford, David W.

1997-01-01

The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N2 at low relative pressures (P/P0). By contrast, EGME shows higher uptakes than N2 on all exchanged clays at all P/P0. The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.

Fabrication of patterned calcium cross-linked alginate hydrogel films and coatings through reductive cation exchange.

PubMed

Bruchet, Marion; Melman, Artem

2015-10-20

Calcium cross-linked alginate hydrogels are widely used in targeted drug delivery, tissue engineering, wound treatment, and other biomedical applications. We developed a method for preparing homogeneous alginate hydrogels cross-linked with Ca(2+) cations using reductive cation exchange in homogeneous iron(III) cross-linked alginate hydrogels. Treatment of iron(III) cross-linked alginate hydrogels with calcium salts and sodium ascorbate results in reduction of iron(III) cations to iron(II) that are instantaneously replaced with Ca(2+) cations, producing homogeneous ionically cross-linking hydrogels. Alternatively, the cation exchange can be performed by photochemical reduction in the presence of calcium chloride using a sacrificial photoreductant. This approach allows fabrication of patterned calcium alginate hydrogels through photochemical patterning of iron(III) cross-linked alginate hydrogel followed by the photochemical reductive exchange of iron cations to calcium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

PubMed

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for estimation of K d values for more structurally complex organic cations to homoionic montmorillonites and to heteroionic soils (mean absolute error of 0.27 log unit). Accordingly, we concluded that the use of phenyltrimethylammonium as a probe compound was a promising means to account for the identity, affinity, and abundance of natural exchange ions in the prediction of organic cation sorption coefficients for environmental solids.

CATION EXCHANGE BETWEEN CELLS AND PLASMA OF MAMMALIAN BLOOD

PubMed Central

Sheppard, C. W.; Martin, W. R.; Beyl, Gertrude

1951-01-01

Sodium and potassium exchange has been studied in the blood of the sheep, dog, cow, and man. The potassium exchange rate in human cells is practically unaltered by increasing the plasma potassium concentration approximately threefold. Comparing the results in different species the exchange rate for potassium shows a rough correlation with the intracellular amount of the element. Expressed in per cent of the cellular content sodium tends to exchange more rapidly than potassium. In three instances the specific activity curves deviate from the simple exponential behavior of a two compartment system. In the exchange of potassium in canine blood the deviation is caused by the presence of a rapidly exchanging fraction in the buffy coat cells. Such an effect does not account for the inhomogeneity of sodium exchange in human blood. PMID:14824508

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences.

PubMed

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences

PubMed Central

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug–fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug–fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid. PMID:25114504

Influence of pine bark particle size and pH on cation exchange capacity

USDA-ARS?s Scientific Manuscript database

Cation exchange capacity (CEC) describes the maximum quantity of cations a soil or substrate can hold while being exchangeable with the soil solution. While CEC has been studied for peat-based substrates, relatively little work has documented factors that affect CEC of pine bark substrates. The ob...

Mineral Separation in a CELSS by Ion-exchange Chromatography

NASA Technical Reports Server (NTRS)

Ballou, E. V.; Spitze, L. A.; Wong, F. W.; Wydeven, T.; Johnson, C. C.

1982-01-01

Operational parameters pertinent to ion exchange chromatography separation were identified. The experiments were performed with 9 mm diameter ion exchange columns and conventional column accessories. The cation separation beds were packed with AG 50W-X2 strong acid cation exchange resin in H(+) form and 200-400 dry mesh particle size. The stripper beds used in some experiments were packed with AG 1-XB strong base cation exchange resin in OH(-) form and 200-400 dry mesh particle size.

Ammonia vapor sensing properties of polyaniline-titanium(IV)phosphate cation exchange nanocomposite.

PubMed

Khan, Asif Ali; Baig, Umair; Khalid, Mohd

2011-02-28

In this study, the electrically conducting polyaniline-titanium(IV)phosphate (PANI-TiP) cation exchange nanocomposite was synthesized by sol-gel method. The cation exchange nanocomposite based sensor for detection of ammonia vapors was developed at room temperature. It was revealed that the sensor showed good reversible response towards ammonia vapors ranging from 3 to 6%. It was found that the sensor with p-toluene sulphonic acid (p-TSA) doped exhibited higher sensing response than hydrochloric acid doped. This sensor has detection limit ≤1% ammonia. The response of resistivity changes of the cation exchange nanocomposite on exposure to different concentrations of ammonia vapors shows its utility as a sensing material. These studies suggest that the cation exchange nanocomposite could be a good material for ammonia sensor at room temperature. Copyright © 2010 Elsevier B.V. All rights reserved.

CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

DOEpatents

Studier, M.H.; Sullivan, J.C.

1959-07-14

A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

Solid-support substrates for plant growth at a lunar base

NASA Technical Reports Server (NTRS)

Ming, D. W.; Galindo, C.; Henninger, D. L.

1990-01-01

Zeoponics is only in its developmental stages at the Johnson Space Center and is defined as the cultivation of plants in zeolite substrates that contain several essential plant growth cations on their exchange sites, and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth anions. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations with the ability to exchange most of their constituent exchange cations as well as hydrate/dehydrate without change to their structural framework. Because zeolites have extremely high cation exchange capabilities, they are very attractive media for plant growth. It is possible to partially or fully saturate plant-essential cations on zeolites. Zeoponic systems will probably have their greatest applications at planetary bases (e.g., lunar bases). Lunar raw materials will have to be located that are suited for the synthesis of zeolites and other exchange resings. Lunar 'soil' simulants have been or are being prepared for zeolite/smectite synthesis and 'soil' dissolution studies.

Measurement of cation exchange capacity (CEC) on natural zeolite by percolation method

NASA Astrophysics Data System (ADS)

Wiyantoko, Bayu; Rahmah, Nafisa

2017-12-01

The cation exchange capacity (CEC)measurement has been carried out in natural zeolite by percolation method. The natural zeolite samples used for cation exchange capacity measurement were activated beforehand with physical activation and chemical activation. The physically activated zeolite was done by calcination process at 600 °C for 4 hours. The natural zeolite was activated chemically by using sodium hydroxide by refluxing process at 60-80 °C for 3 hours. In summary, cation exchange capacity (CEC) determination was performed by percolation, distillation and titration processes. Based on the measurement that has been done, the exchange rate results from physical activated and chemical activated of natural zeolite were 181.90cmol (+)/kg and 901.49cmol (+)/kg respectively.

Systematic Interpolation Method Predicts Antibody Monomer-Dimer Separation by Gradient Elution Chromatography at High Protein Loads.

PubMed

Creasy, Arch; Reck, Jason; Pabst, Timothy; Hunter, Alan; Barker, Gregory; Carta, Giorgio

2018-05-29

A previously developed empirical interpolation (EI) method is extended to predict highly overloaded multicomponent elution behavior on a cation exchange (CEX) column based on batch isotherm data. Instead of a fully mechanistic model, the EI method employs an empirically modified multicomponent Langmuir equation to correlate two-component adsorption isotherm data at different salt concentrations. Piecewise cubic interpolating polynomials are then used to predict competitive binding at intermediate salt concentrations. The approach is tested for the separation of monoclonal antibody monomer and dimer mixtures by gradient elution on the cation exchange resin Nuvia HR-S. Adsorption isotherms are obtained over a range of salt concentrations with varying monomer and dimer concentrations. Coupled with a lumped kinetic model, the interpolated isotherms predict the column behavior for highly overloaded conditions. Predictions based on the EI method showed good agreement with experimental elution curves for protein loads up to 40 mg/mL column or about 50% of the column binding capacity. The approach can be extended to other chromatographic modalities and to more than two components. This article is protected by copyright. All rights reserved.

Anion exchange membrane

DOEpatents

Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

2013-05-07

An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

Cu3-xP Nanocrystals as a Material Platform for Near-Infrared Plasmonics and Cation Exchange Reactions

PubMed Central

2015-01-01

Synthesis approaches to colloidal Cu3P nanocrystals (NCs) have been recently developed, and their optical absorption features in the near-infrared (NIR) have been interpreted as arising from a localized surface plasmon resonance (LSPR). Our pump–probe measurements on platelet-shaped Cu3-xP NCs corroborate the plasmonic character of this absorption. In accordance with studies on crystal structure analysis of Cu3P dating back to the 1970s, our density functional calculations indicate that this material is substoichiometric in copper, since the energy of formation of Cu vacancies in certain crystallographic sites is negative, that is, they are thermodynamically favored. Also, thermoelectric measurements point to a p-type behavior of the majority carriers from films of Cu3-xP NCs. It is likely that both the LSPR and the p-type character of our Cu3-xP NCs arise from the presence of a large number of Cu vacancies in such NCs. Motivated by the presence of Cu vacancies that facilitate the ion diffusion, we have additionally exploited Cu3-xP NCs as a starting material on which to probe cation exchange reactions. We demonstrate here that Cu3-xP NCs can be easily cation-exchanged to hexagonal wurtzite InP NCs, with preservation of the anion framework (the anion framework in Cu3-xP is very close to that of wurtzite InP). Intermediate steps in this reaction are represented by Cu3-xP/InP heterostructures, as a consequence of the fact that the exchange between Cu+ and In3+ ions starts from the peripheral corners of each NC and gradually evolves toward the center. The feasibility of this transformation makes Cu3-xP NCs an interesting material platform from which to access other metal phosphides by cation exchange. PMID:25960605

Sorption of fluoroquinolones and sulfonamides in 13 Brazilian soils.

PubMed

Leal, Rafael Marques Pereira; Alleoni, Luis Reynaldo Ferracciú; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges

2013-08-01

Animal production is a leading economic activity in Brazil and antibiotics are widely used. However, the occurrence, behavior, and impacts of antibiotics in Brazilian soils are still poorly known. We evaluated the sorption behavior of four fluoroquinolones (norfloxacin, ciprofloxacin, danofloxacin, and enrofloxacin) and five sulfonamides (sulfadiazine, sulfachloropyridazine, sulfamethoxazole, sulfadimidine, and sulfathiazole) in 13 Brazilian soils with contrasting physical, chemical, and mineralogical properties. Fluoroquinolone sorption was very high (Kd≥544 L kg(-1)) whereas sulfonamide sorption ranged from low to high (Kd=0.7-70.1 L kg(-1)), consistent with previous reports in the literature. Soil texture and cation exchange capacity were the soil attributes that most affected sorption. Cation exchange was the most important sorption mechanism for the fluoroquinolones in highly weathered tropical soils, although cation bridging and ion pairing could not be ruled out. Hydrophobic partition played an important role in the sorption of the sulfonamides, but sorption was also affected by non-hydrophobic interactions with organic and/or mineral surfaces. Sorption for both compound classes tended to be higher in soils with high Al and Fe oxihydroxide contents, but they were not correlated with Kd values. No direct effect of soil pH was seen. The fluoroquinolones are not expected to leach even in worst-case scenarios (soils rich in sand and poor in organic carbon), whereas soil attributes dictate leaching potential for the sulfonamides. Copyright © 2013 Elsevier Ltd. All rights reserved.

Comparison of amine-selective properties of weak and strong cation-exchangers.

PubMed

Stenholm, Ake; Lindgren, Helena; Shaffie, Juliana

2006-09-22

The capacity of several weak and strong cation-exchangers to adsorb 2-diethylaminoethanol (DEAE) and (2,3-hydroxypropyl) trimethylammonium chloride (HPMAC) from sodium-containing process water streams, and the ease of subsequently eluting the amines and regenerating the exchangers, were investigated. (2,3-hydroxypropyl) trimethylammonium chloride was enriched 40-fold compared with the initial amine/sodium-ratio in the bulk fluid by Amberlite IRC-50. The highest selectivity for 2-diethylaminoethanol (26-fold) was provided by Imac HP336. Neither of the selected strong cation-exchangers showed any selectivity towards 2-diethylaminoethanol, but they enriched (2,3-hydroxypropyl) trimethylammonium chloride approximately three to four fold. These findings suggest that weak cation-exchangers (WCX) could be readily used for the selective removal of these or similar amines from sodium-containing process waters.

Cation Exchange in the Presence of Oil in Porous Media

PubMed Central

2017-01-01

Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media. PMID:28580442

ERYTHROPOIETIC FACTOR PURIFICATION

DOEpatents

White, W.F.; Schlueter, R.J.

1962-05-01

A method is given for purifying and concentrating the blood plasma erythropoietic factor. Anemic sheep plasma is contacted three times successively with ion exchange resins: an anion exchange resin, a cation exchange resin at a pH of about 5, and a cation exchange resin at a pH of about 6. (AEC)

Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Beberwyck, Brandon James

Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be made for its adoption as a routine synthetic approach.

[Determination of soil exchangeable base cations by using atomic absorption spectrophotometer and extraction with ammonium acetate].

PubMed

Zhang, Yu-ge; Xiao, Min; Dong, Yi-hua; Jiang, Yong

2012-08-01

A method to determine soil exchangeable calcium (Ca), magnesium (Mg), potassium (K), and sodium (Na) by using atomic absorption spectrophotometer (AAS) and extraction with ammonium acetate was developed. Results showed that the accuracy of exchangeable base cation data with AAS method fits well with the national standard referential soil data. The relative errors for parallel samples of exchangeable Ca and Mg with 66 pair samples ranged from 0.02%-3.14% and 0.06%-4.06%, and averaged to be 1.22% and 1.25%, respectively. The relative errors for exchangeable K and Na with AAS and flame photometer (FP) ranged from 0.06%-8.39% and 0.06-1.54, and averaged to be 3.72% and 0.56%, respectively. A case study showed that the determination method for exchangeable base cations by using AAS was proven to be reliable and trustable, which could reflect the real situation of soil cation exchange properties in farmlands.

Molecular dynamics simulations of cesium adsorption on illite nanoparticles.

PubMed

Lammers, Laura N; Bourg, Ian C; Okumura, Masahiko; Kolluri, Kedarnath; Sposito, Garrison; Machida, Masahiko

2017-03-15

The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs ( 134 Cs, 135 Cs, 137 Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model. Copyright © 2016 Elsevier Inc. All rights reserved.

Antibacterial activity of the soil-bound antimicrobials oxytetracycline and ofloxacin.

PubMed

Peng, Feng-Jiao; Zhou, Li-Jun; Ying, Guang-Guo; Liu, You-Sheng; Zhao, Jian-Liang

2014-04-01

Soil contamination of antimicrobials has become an increasing concern because of the potential risks to the soil microbial ecosystem and human health. The present study investigated sorption and desorption behaviors of oxytetracycline (OTC) and ofloxacin (OFL) in 3 typical soils (A, B, and C), and evaluated the antibacterial activity of soil-adsorbed compounds to a pure sensitive strain Escherichia coli ATCC 25922. The results showed different sorption and desorption behaviors of OTC and OFL in the 3 soils, behaviors that were mainly influenced by soil organic matter content and cation exchange capacity (CEC) as well as pH value. In addition, complexation and cation-exchange reactions were shown to be the main sorption mechanisms. Strong adsorption was found in soil B (with a high organic matter content) and in soil C (with high CEC), whereas enhanced desorption was observed in soil A (with low organic matter content). The results also demonstrated that soil-bound antimicrobials retained antibacterial activity toward E. coli. Opposite patterns of antibacterial activity were found for the 2 antimicrobials in the 3 soils: A>B>C for OFL; and C>B>A for OTC. This finding suggests that soil-bound antimicrobials could still exert selective pressure on soil bacteria although less effectively in comparison with the dissolved forms. © 2014 SETAC.

Metal cation exchange reactions of ore minerals in Fe-Mn crusts of the Marcus Wake Rise (Pacific Ocean) in aqueous-salt solutions

NASA Astrophysics Data System (ADS)

Novikov, G. V.; Bogdanova, O. Yu.; Melnikov, M. E.; Drozdova, A. N.; Lobus, N. V.; Shulga, N. A.

2017-12-01

It is shown that the reaction ability of metal cations of ore minerals in Fe-Mn crusts of the Marcus Wake Rise increases in the following manner: (Co2+ < Cu2+ < Ni2+) < (Mg2+ < Mn2+ < K+ ≈ Ca2+ ≈ Na+). The composition of the exchange complex of the ore minerals is constant and includes these metal cations. Ca2+ and Na+ are major contributors to the exchange capacity of the ore minerals. The capacity of the ore minerals by cations of alkali and base metals is 0.43-0.60 and 2.08-2.70 mg-equiv/g, respectively. The exchange capacity of the ore minerals by cations of base metals increases linearly with the increase in the MnO2 content of the crust and does not depend on the geographical locations of the Marcus Wake guyots.

Huntingtin regulates Ca(2+) chemotaxis and K(+)-facilitated cAMP chemotaxis, in conjunction with the monovalent cation/H(+) exchanger Nhe1, in a model developmental system: insights into its possible role in Huntington׳s disease.

PubMed

Wessels, Deborah; Lusche, Daniel F; Scherer, Amanda; Kuhl, Spencer; Myre, Michael A; Soll, David R

2014-10-01

Huntington׳s disease is a neurodegenerative disorder, attributable to an expanded trinucleotide repeat in the coding region of the human HTT gene, which encodes the protein huntingtin. These mutations lead to huntingtin fragment inclusions in the striatum of the brain. However, the exact function of normal huntingtin and the defect causing the disease remain obscure. Because there are indications that huntingtin plays a role in Ca(2+) homeostasis, we studied the deletion mutant of the HTT ortholog in the model developmental system Dictyostelium discoideum, in which Ca(2+) plays a role in receptor-regulated behavior related to the aggregation process that leads to multicellular morphogenesis. The D. discoideum htt(-)-mutant failed to undergo both K(+)-facilitated chemotaxis in spatial gradients of the major chemoattractant cAMP, and chemotaxis up a spatial gradient of Ca(2+), but behaved normally in Ca(2+)-facilitated cAMP chemotaxis and Ca(2+)-dependent flow-directed motility. This was the same phenotypic profile of the null mutant of Nhel, a monovalent cation/H(+)exchanger. The htt(-)-mutant also failed to orient correctly during natural aggregation, as was the case for the Nhel mutant. Moreover, in a K(+)-based buffer the normal localization of actin was similarly defective in both htt(-) and nhe1(-) cells in a K(+)-based buffer, and the normal localization of Nhe1 was disrupted in the htt(-) mutant. These observations demonstrate that Htt and Nhel play roles in the same specific cation-facilitated behaviors and that Nhel localization is directly or indirectly regulated by Htt. Similar cation-dependent behaviors and a similar relationship between Htt and Nhe1 have not been reported for mammalian neurons and deserves investigation, especially as it may relate to Huntington׳s disease. Copyright © 2014 Elsevier Inc. All rights reserved.

Synthesis and Characterization of Perfluoro Quaternary Ammonium Anion Exchange Membranes

DTIC Science & Technology

2012-01-01

study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer with various quaternary ammonium cations attached with...ammonium anion exchange membranes Report Title ABSTRACT In this study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer...exchange membranes were prepared from the perfluorinated 3M ionomer with vari- ous quaternary ammonium cations attached with sulfonamide linkage. The

Recovery process for electroless plating baths

DOEpatents

Anderson, Roger W.; Neff, Wayne A.

1992-01-01

A process for removing, from spent electroless metal plating bath solutions, accumulated byproducts and counter-ions that have deleterious effects on plating. The solution, or a portion thereof, is passed through a selected cation exchange resin bed in hydrogen form, the resin selected from strong acid cation exchangers and combinations of intermediate acid cation exchangers with strong acid cation exchangers. Sodium and nickel ions are sorbed in the selected cation exchanger, with little removal of other constituents. The remaining solution is subjected to sulfate removal through precipitation of calcium sulfate hemihydrate using, sequentially, CaO and then CaCO.sub.3. Phosphite removal from the solution is accomplished by the addition of MgO to form magnesium phosphite trihydrate. The washed precipitates of these steps can be safely discarded in nontoxic land fills, or used in various chemical industries. Finally, any remaining solution can be concentrated, adjusted for pH, and be ready for reuse. The plating metal can be removed from the exchanger with sulfuric acid or with the filtrate from the magnesium phosphite precipitation forming a sulfate of the plating metal for reuse. The process is illustrated as applied to processing electroless nickel plating baths.

Recovery process for electroless plating baths

DOEpatents

Anderson, R.W.; Neff, W.A.

1992-05-12

A process is described for removing, from spent electroless metal plating bath solutions, accumulated byproducts and counter-ions that have deleterious effects on plating. The solution, or a portion thereof, is passed through a selected cation exchange resin bed in hydrogen form, the resin selected from strong acid cation exchangers and combinations of intermediate acid cation exchangers with strong acid cation exchangers. Sodium and nickel ions are sorbed in the selected cation exchanger, with little removal of other constituents. The remaining solution is subjected to sulfate removal through precipitation of calcium sulfate hemihydrate using, sequentially, CaO and then CaCO[sub 3]. Phosphite removal from the solution is accomplished by the addition of MgO to form magnesium phosphite trihydrate. The washed precipitates of these steps can be safely discarded in nontoxic land fills, or used in various chemical industries. Finally, any remaining solution can be concentrated, adjusted for pH, and be ready for reuse. The plating metal can be removed from the exchanger with sulfuric acid or with the filtrate from the magnesium phosphite precipitation forming a sulfate of the plating metal for reuse. The process is illustrated as applied to processing electroless nickel plating baths. 18 figs.

Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil.

PubMed

Barzen-Hanson, Krista A; Davis, Shannon E; Kleber, Markus; Field, Jennifer A

2017-11-07

During fire-fighter training, equipment testing, and emergency responses with aqueous film-forming foams (AFFFs), milligrams per liter concentrations of anionic, zwitterionic, and cationic per- and polyfluoroalkyl substances (PFASs) enter the environment. Because the behavior of zwitterionic and cationic PFASs in the subsurface is unknown, batch sorption experiments were conducted using National Foam AFFF, which contains anionic fluorotelomer sulfonates (FtSs), zwitterionic fluorotelomer sulfonamido betaines (FtSaBs), and cationic 6:2 fluorotelomer sulfonamido amine (FtSaAm). Sorption of the FtSs, FtSaBs, and 6:2 FtSaAm to six soils with varying organic carbon, effective cation-exchange capacity, and anion-exchange capacity was evaluated to determine sorption mechanisms. Due to the poor recovery of the FtSaBs and 6:2 FtSaAm with published PFAS soil extraction methods, a new soil extraction method was developed to achieve good (90-100%) recoveries. The 6:2 FtSaAm was depleted from the aqueous phase in all but one soil, which is attributed to electrostatic and hydrophobic interactions. Sorption of the FtSs was driven by hydrophobic interactions, while the FtSaBs behave more like cations that strongly associate with the solid phase relative to groundwater. Thus, the sorption mechanisms of the FtSs, FtSaBs, and 6:2 FtSaAm are more complex than expected and cannot be predicted by bulk soil properties.

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

Comparative analysis of cation/proton antiporter superfamily in plants.

PubMed

Ye, Chu-Yu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

2013-06-01

The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant species was reported. We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240 members are separated into three families, i.e., Na(+)/H(+) exchangers, K(+) efflux antiporters, and cation/H(+) exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H(+) exchangers in the examined angiosperm species. Sliding window analysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and found most motifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants. Copyright © 2013 Elsevier B.V. All rights reserved.

Nongeminate Radiative Recombination of Free Charges in Cation-Exchanged PbS Quantum Dot Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Ashley R.; Beard, Matthew C.; Johnson, Justin C.

2016-06-01

Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films.more » We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.« less

Nongeminate radiative recombination of free charges in cation-exchanged PbS quantum dot films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Ashley R.; Beard, Matthew C.; Johnson, Justin C.

2016-06-01

Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films.more » We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.« less

A Scale Model of Cation Exchange for Classroom Demonstration.

ERIC Educational Resources Information Center

Guertal, E. A.; Hattey, J. A.

1996-01-01

Describes a project that developed a scale model of cation exchange that can be used for a classroom demonstration. The model uses kaolinite clay, nails, plywood, and foam balls to enable students to gain a better understanding of the exchange complex of soil clays. (DDR)

Cation exchange assisted binding-elution strategy for enzymatic synthesis of human milk oligosaccharides (HMOs).

PubMed

Zhu, Hailiang; Wu, Zhigang; Gadi, Madhusudhan Reddy; Wang, Shuaishuai; Guo, Yuxi; Edmunds, Garrett; Guan, Wanyi; Fang, Junqiang

2017-09-15

A cation exchange assisted binding-elution (BE) strategy for enzymatic synthesis of human milk oligosaccharides (HMOs) was developed. An amino linker was used to provide the cation ion under acidic condition which can be readily bound to cation exchange resin and then eluted off by saturated ammonium bicarbonate. Ammonium bicarbonate in the collections was easily removed by vacuum evaporation. This strategy circumvented the incompatible issue between glycosyltransferases and solid support or large polymers, and no purification was needed for intermediate products. With current approach, polyLacNAc backbones of HMOs and fucosylated HMOs were synthesized smoothly. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermodynamic derivation of open circuit voltage in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Pavelka, Michal; Wandschneider, Frank; Mazur, Petr

2015-10-01

Open circuit voltage of vanadium redox flow batteries is carefully calculated using equilibrium thermodynamics. This analysis reveals some terms in the Nernst relation which are usually omitted in literature. Due to the careful thermodynamic treatment, all uncertainties about the form of Nernst relation are removed except for uncertainties in activity coefficients of particular species. Moreover, it is shown (based again on equilibrium thermodynamics) that batteries with anion-exchange membranes follow different Nernst relation than batteries with cation-exchange membranes. The difference is calculated, and it is verified experimentally that the formula for anion-exchange membranes describes experiments with anion-exchange membranes better than the corresponding formula for cation-exchange membranes. In summary, careful thermodynamic calculation of open circuit voltage of vanadium redox flow batteries is presented, and the difference between voltage for anion-exchange and cation-exchange membranes is revealed.

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

PubMed Central

2014-01-01

We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

Roles of cation valance and exchange on the retention and colloid-facilitated transport of functionalized multi-walled carbon nanotubes in a natural soil

USDA-ARS?s Scientific Manuscript database

Saturated soil column experiments were conducted to investigate the transport, retention, and release behavior of a low concentration (1 mg L-1) of functionalized 14C-labeled multi-walled carbon nanotubes (MWCNTs) in a natural soil under various solution chemistries. Breakthrough curves (BTCs) for M...

Publications - GMC 319 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 319 Publication Details Title: Porotechnology data and cation exchange capacity data Authors and cation exchange capacity data: Alaska Division of Geological & Geophysical Surveys Geologic

Prediction of Intrinsic Cesium Desorption from Na-Smectite in Mixed Cation Solutions.

PubMed

Fukushi, Keisuke; Fukiage, Tomo

2015-09-01

Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na(+) and divalent cations (Ca(2+) and Mg(2+)). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na(+)-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na(+) concentrations facilitate Cs desorption because Na(+) serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na(+) fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na(+) concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water.

Zebrafish ("Danio rerio") endomembrane antiporter similar to a yeast cation/H(+) transporter is required for neural crest development

USDA-ARS?s Scientific Manuscript database

CAtion/H (+) eXchangers (CAXs) are integral membrane proteins that transport Ca (2+) or other cations by exchange with protons. While several yeast and plant CAX proteins have been characterized, no functional analysis of a vertebrate CAX homologue has yet been reported. In this study, we further ch...

Trends in Effective Diffusion Coefficients for Ion-exchange Strengthening of Soda Lime Silicate Glasses

NASA Astrophysics Data System (ADS)

Karlsson, Stefan; Wondraczek, Lothar; Ali, Sharafat; Jonson, Bo

2017-04-01

Monovalent cations enable efficient ion exchange processes due to their high mobility in silicate glasses. Numerous properties can be modified in this way, e.g., mechanical, optical, electrical or chemical performance. In particular, alkali cation exchange has received significant attention, primarily with respect to introducing compressive stress into the surface region of a glass, which increases mechanical durability. However, most of the present applications rely on specifically tailored matrix compositions in which the cation mobility is enhanced. This largely excludes the major area of soda lime silicates (SLS) such as are commodity in almost all large-scale applications of glasses. Basic understanding of the relations between structural parameters and the effective diffusion coefficients may help to improve ion-exchanged SLS glass products, on the one hand in terms of obtainable strength and on the other in terms of cost. In the present paper, we discuss the trends in the effective diffusion coefficients when exchanging Na+ for various monovalent cations (K+, Cu+, Ag+, Rb+ and Cs+) by drawing relations to physico-chemical properties. Correlations of effective diffusion coefficients were found for the bond dissociation energy and the electronic cation polarizability, indicating that localization and rupture of bonds are of importance for the ion exchange rate.

Forging Colloidal Nanostructures via Cation Exchange Reactions

PubMed Central

2016-01-01

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

Isotopic generator for bismuth-212 and lead-212 based on radium

DOEpatents

Hines, J.J.; Atcher, R.W.; Friedman, A.M.

1985-01-30

Disclosed are method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

Isotopic generator for bismuth-212 and lead-212 from radium

DOEpatents

Atcher, Robert W.; Friedman, Arnold M.; Hines, John

1987-01-01

A method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

Forging Colloidal Nanostructures via Cation Exchange Reactions.

PubMed

De Trizio, Luca; Manna, Liberato

2016-09-28

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments.

PubMed

Steefel, Carl I; Carroll, Susan; Zhao, Pihong; Roberts, Sarah

2003-12-01

Cs+ transport experiments carried out in columns packed with uncontaminated Hanford formation sediment from the SX tank farm provide strong support for the use of a multisite, multicomponent cation exchange model to describe Cs+ migration in the Hanford vadose zone. The experimental results indicate a strong dependence of the effective Cs+ Kd on the concentrations of other cations, including Na+ that is present at high to extremely high concentrations in fluids leaking from the Hanford SX tanks. A strong dependence of the Cs+ Kd on the aqueous Cs+ concentration is also apparent, with retardation of Cs+ increasing from a value of 41 at a Cs+ concentration of 10(-4) M in the feed solution to as much as 282 at a Cs+ concentration of 5x10(-7) M, all in a background of 1 M NaNO3. The total cation exchange capacity (CEC) of the Hanford sediment was determined using 22Na isotopic equilibrium exchange in a flow-through column experiment. The value for the CEC of 120 microeq/g determined with this method is compatible with a value of 121.9 microeq/g determined by multi-cation elution. While two distinct exchange sites were proposed by Zachara et al. [Geochim. Cosmochim. Acta 66 (2002) 193] based on binary batch exchange experiments, a third site is proposed in this study to improve the fit of the Cs+-Na+ and Cs+-Ca+ exchange data and to capture self-sharpened Cs+ breakthrough curves at low concentrations of Cs+. Two of the proposed exchange sites represent frayed edge sites (FES) on weathered micas and constitute 0.02% and 0.22% of the total CEC. Both of the FES show a very strong selectivity for Cs+ over Na+ (K(Na-Cs)=10(7.22) and 10(4.93), respectively). The third site, accounting for over 99% of the total CEC, is associated with planar sites on expansible clays and shows a smaller Na+-Cs+ selectivity coefficient of 10(1.99). Parameters derived from a fit of binary batch experiments alone tend to under predict Cs+ retardation in the column experiments. The transport experiments indicate 72-90% of the Cs+ sorbed in experiments targeting exchange on FES was desorbed over a 10- and 24-day period, respectively. At high Cs+ concentrations, where sorption is controlled primarily by exchange on planar sites, 95% of the Cs+ desorption was desorbed. Most of the difficulty in desorbing Cs+ from FES is a result of the extremely high selectivity of these sites for Cs+, although truly irreversible sorption as high as 23% was suggested in one experiment. The conclusion that Cs+ exchange is largely reversible in a thermodynamic sense is supported by the ability to match Cs+ desorption curves almost quantitatively with an equilibrium reactive transport simulation. The model for Cs+ retardation developed here qualitatively explains the behavior of Cs+ in the Hanford vadose zone underneath a variety of leaking tanks with differing salt concentrations. The high selectivity of FES for Cs+ implies that future desorption and migration is very unlikely to occur under natural recharge conditions.

Cation Exchange Water Softeners

EPA Pesticide Factsheets

WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

Synthesis, characterization and analytical application of hybrid; acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions.

PubMed

Nabi, Syed A; Shalla, Aabid H

2009-04-30

A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na(+) ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 degrees C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb(2+) ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb(2+) has been selectively removed from synthetic mixtures containing Mg(2+), Ca(2+), Sr(2+), Zn(2+) and Cu(2+), Al(3+), Ni(2+), Fe(3+). In order to demonstrate practical utility of the material quantitative separation of the Cu(2+) and Zn(2+) in brass sample has been achieved on its columns.

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

PubMed

Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

2017-05-02

Trinuclear versus dinuclear heterodimetallic U V O 2 + Co 2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

Surfactant modified zeolite as amphiphilic and dual-electronic adsorbent for removal of cationic and oxyanionic metal ions and organic compounds.

PubMed

Tran, Hai Nguyen; Viet, Pham Van; Chao, Huan-Ping

2018-01-01

A hydrophilic Y zeolite was primarily treated with sodium hydroxide to enhance its cation exchange capacity (Na-zeolite). The organo-zeolite (Na-H-zeolite) was prepared by a modification process of the external surface of Na-zeolite with a cationic surfactant (hexadecyltrimethylammonium; HDTMA). Three adsorbents (i.e., pristine zeolite, Na-zeolite, and Na-H-zeolite) were characterized with nitrogen adsorption/desorption isotherms, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, cation exchange capacities, and zeta potential. Results demonstrated that HDTMA can be adsorbed on the surface of Na-zeolite to form patchy bilayers. The adsorption capacity of several hazardous pollutants (i.e., Pb 2+ , Cu 2+ , Ni 2+ , Cr 2 O 7 2- , propylbenzene, ethylbenzene, toluene, benzene, and phenol) onto Na-H-zeolite was investigated in a single system and multiple-components. Adsorption isotherm was measured to further understand the effects of the modification process on the adsorption behaviors of Na-H-zeolite. Adsorption performances indicated that Na-H-zeolite can simultaneously adsorb the metal cations (on the surface not covered by HDTMA), oxyanions (on the surface covered by HDTMA). Na-H-zeolite also exhibited both hydrophilic and hydrophobic surfaces to uptake organic compounds with various water solubilities (from 55 to 75,000mg/L). It was experimentally concluded that Na-H-zeolite is a potential dual-electronic and amphiphilic adsorbent for efficiently removing a wide range of potentially toxic pollutants from aquatic environments. Copyright © 2017 Elsevier Inc. All rights reserved.

Effects of silicate weathering on water chemistry in forested, upland, felsic terrane of the USA

NASA Astrophysics Data System (ADS)

Stauffer, Robert E.; Wittchen, Bruce D.

1991-11-01

We use data from the US EPA National Surface Water Survey (NSWS), the USGS Bench-Mark Station monitoring program, and the National Acid Deposition Program (NADP) to evaluate the role of weathering in supplying base cations to surface waters in forested, upland, felsic terrane of the northeastern, northcentral, and northwestern (Idaho batholith) United States. Multivariate regression reveals differential effects of discharge on individual base cations and silica, but no secular trend in the Ca/Na denudation rate over 24 yr (1965-1988) for the Wild River catchment in the White Mountains. Because the turn-over time for Na in the soil-exchange complex is only ca. 1.5 yr, the long-term behavior of the ratios Ca/Na and Si/Na in waters leaving this catchment indicates that weathering is compensating for base cation export. In every subregion, Ca and Mg concentrations in lakes are statistically linked to nonmarine Na, but the median Ca/Na ratio is greater than the ratio in local plagioclase. We attribute this inequality to nonstoichiometric weathering of calcium in juvenile (formerly glaciated) terrane, not to leaching of exchangeable cations by SO 4, because intraregional and cross-regional statistical analysis reveals no effect of atmospherically derived sulfate ion. The median base cation denudation rates (meq m -2 yr -1) for these American lake regions are: Maine granites (108); western Adirondack felsic gneiss (85); Vermilion batholith (42); Idaho batholith (52). The regional rates are high enough to compensate for present wet deposition of acidifying anions except in some vulnerable lake watersheds in the western Adirondacks.

Preparation of immunoglobulin Y from egg yolk using ammonium sulfate precipitation and ion exchange chromatography.

PubMed

Ko, K Y; Ahn, D U

2007-02-01

The objective of this study was to develop an economical, simple, and large-scale separation method for IgY from egg yolk. Egg yolk diluted with 9 volumes of cold water was centrifuged after adjusting the pH to 5.0. The supernatant was added with 0.01% charcoal or 0.01% carrageenan and centrifuged at 2,800 x g for 30 min. The supernatant was filtered through a Whatman no. 1 filter paper and then the filtrate was concentrated to 20% original volume using ultrafiltration. The concentrated solution was further purified using either cation exchange chromatography or ammonium sulfate precipitation. For the cation exchange chromatography method, the concentrated sample was loaded onto a column equilibrated with 20 mM citrate-phosphate buffer at pH 4.8 and eluted with 200 mM citrate-phosphate buffer at pH 6.4. For the ammonium sulfate precipitation method, the concentrated sample was twice precipitated with 40% ammonium sulfate solution at pH 9.0. The yield and purity of IgY were determined by ELISA and electrophoresis. The yield of IgY from the cation exchange chromatography method was 30 to 40%, whereas that of the ammonium sulfate precipitation was 70 to 80%. The purity of IgY from the ammonium sulfate method was higher than that of the cation exchange chromatography. The cation exchange chromatography could handle only a small amount of samples, whereas the ammonium sulfate precipitation could handle a large volume of samples. This suggests that ammonium sulfate precipitation was a more efficient and useful purification method than cation exchange chromatography for the large-scale preparation of IgY from egg yolk.

Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

PubMed

Bhaskar, M; Surekha, M; Suma, N

2018-02-01

The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

Spectroscopic study of carbaryl sorption on smectite from aqueous suspension.

PubMed

de Oliveira, Maurilio Fernandes; Johnston, Cliff T; Premachandra, G S; Teppen, Brian J; Li, Hui; Laird, David A; Zhu, Dongqiang; Boyd, Stephen A

2005-12-01

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.

Cation exchange in a glacial till drumlin at a road salt storage facility

NASA Astrophysics Data System (ADS)

Ostendorf, David W.; Xing, Baoshan; Kallergis, Niki

2009-05-01

We use laboratory and field data to calibrate existing geochemical and transport models of cation exchange induced by contamination of an unconfined aquifer at a road salt storage facility built upon a glacial till drumlin in eastern Massachusetts. A Gaines and Thomas selectivity coefficient K models the equilibrium sodium and divalent cation distribution in the groundwater and solid matrix, while an existing method of characteristics model describes the advective transport of total dissolved cations and sorbed sodium. Laboratory isotherms of split spoon soil samples from the drumlin calibrate K with an average value of 0.0048 (L/g) 1/2 for a measured cation exchange capacity of 0.057 meq/g dry soil. Ten years of monitoring well data document groundwater flow and the advection of conservative chloride due to outdoor storage and handling of road salt at the site. The monitoring well cation data and retarded transport model offer an independent K calibration of 0.0040 to 0.0047 (L/g) 1/2: the consistency of the field and laboratory selectivity coefficient calibrations endorse this application of the Gaines and Thomas and method of characteristics models. The advancing deicing agent plume releases divalent cations from the till into the groundwater, so that monitoring well samples do not reflect the chemical composition of the road salt. In this regard, dissolved divalent cation milliequivalent concentrations are as high as 80% of the total dissolved cationic concentrations in the salt contaminated monitoring well samples, far greater than their 2.5% level in the road salt stored at the site. Cation exchange can thus obscure attempts to hindcast stored road salt sodium water table concentration from monitoring well sample stoichiometry, or to predict sodium impacts on groundwater or receiving stream quality downgradient of the well.

Cation exchange in a glacial till drumlin at a road salt storage facility.

PubMed

Ostendorf, David W; Xing, Baoshan; Kallergis, Niki

2009-05-12

We use laboratory and field data to calibrate existing geochemical and transport models of cation exchange induced by contamination of an unconfined aquifer at a road salt storage facility built upon a glacial till drumlin in eastern Massachusetts. A Gaines and Thomas selectivity coefficient K models the equilibrium sodium and divalent cation distribution in the groundwater and solid matrix, while an existing method of characteristics model describes the advective transport of total dissolved cations and sorbed sodium. Laboratory isotherms of split spoon soil samples from the drumlin calibrate K with an average value of 0.0048 (L/g)(1/2) for a measured cation exchange capacity of 0.057 meq/g dry soil. Ten years of monitoring well data document groundwater flow and the advection of conservative chloride due to outdoor storage and handling of road salt at the site. The monitoring well cation data and retarded transport model offer an independent K calibration of 0.0040 to 0.0047 (L/g)(1/2): the consistency of the field and laboratory selectivity coefficient calibrations endorse this application of the Gaines and Thomas and method of characteristics models. The advancing deicing agent plume releases divalent cations from the till into the groundwater, so that monitoring well samples do not reflect the chemical composition of the road salt. In this regard, dissolved divalent cation milliequivalent concentrations are as high as 80% of the total dissolved cationic concentrations in the salt contaminated monitoring well samples, far greater than their 2.5% level in the road salt stored at the site. Cation exchange can thus obscure attempts to hindcast stored road salt sodium water table concentration from monitoring well sample stoichiometry, or to predict sodium impacts on groundwater or receiving stream quality downgradient of the well.

Cation-Exchanged Zeolitic Chalcogenides for CO2 Adsorption.

PubMed

Yang, Huajun; Luo, Min; Chen, Xitong; Zhao, Xiang; Lin, Jian; Hu, Dandan; Li, Dongsheng; Bu, Xianhui; Feng, Pingyun; Wu, Tao

2017-12-18

We report here the intrinsic advantages of a special family of porous chalcogenides for CO 2 adsorption in terms of high selectivity of CO 2 /N 2 , large uptake capacity, and robust structure due to their first-ever unique integration of the chalcogen-soft surface, high porosity, all-inorganic crystalline framework, and the tunable charge-to-volume ratio of exchangeable cations. Although tuning the CO 2 adsorption properties via the type of exchangeable cations has been well-studied in oxides and MOFs, little is known about the effects of inorganic exchangeable cations in porous chalcogenides, in part because ion exchange in chalcogenides can be very sluggish and incomplete due to their soft character. We have demonstrated that, through a methodological change to progressively tune the host-guest interactions, both facile and nearly complete ion exchange can be accomplished. Herein, a series of cation-exchanged zeolitic chalcogenides (denoted as M@RWY) were studied for the first time for CO 2 adsorption. Samples were prepared through a sequential ion-exchange strategy, and Cs + -, Rb + -, and K + -exchanged samples demonstrated excellent CO 2 adsorption performance. Particularly, K@RWY has the superior CO 2 /N 2 selectivity with the N 2 adsorption even undetected at either 298 or 273 K. It also has the large uptake of 6.3 mmol/g (141 cm 3 /g) at 273 K and 1 atm with an isosteric heat of 35-41 kJ mol -1 , the best among known porous chalcogenides. Moreover, it permits a facile regeneration and exhibits an excellent recyclability, as shown by the multicycling adsorption experiments. Notably, K@RWY also demonstrates a strong tolerance toward water.

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

PubMed

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

Divalent Cation Removal by Donnan Dialysis for Improved Reverse Electrodialysis.

PubMed

Rijnaarts, Timon; Shenkute, Nathnael T; Wood, Jeffery A; de Vos, Wiebe M; Nijmeijer, Kitty

2018-05-07

Divalent cations in feedwater can cause significant decreases in efficiencies for membrane processes, such as reverse electrodialysis (RED). In RED, power is harvested from the mixing of river and seawater, and the obtainable voltage is reduced and the resistance is increased if divalent cations are present. The power density of the RED process can be improved by removing divalent cations from the fresh water. Here, we study divalent cation removal from fresh water using seawater as draw solution in a Donnan dialysis (DD) process. In this way, a membrane system with neither chemicals nor electrodes but only natural salinity gradients can be used to exchange divalent cations. For DD, the permselectivity of the cation exchange membrane is found to be crucial as it determines the ability to block salt leakage (also referred to as co-ion transport). Operating DD using a membrane stack achieved a 76% reduction in the divalent cation content in natural fresh water with residence times of just a few seconds. DD pretreated fresh water was then used in a RED process, which showed improved gross and net power densities of 9.0 and 6.3%, respectively. This improvement is caused by a lower fresh water resistance (at similar open circuit voltages), due to exchange of divalent for monovalent cations.

Elucidation of Two Giants: Challenges to Thick-shell Synthesis in CdSe/ZnSe and ZnSe/CdS Core/Shell Quantum Dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acharya, Krishna P.; Nguyen, Hue M.; Paulite, Melissa

2015-03-06

Core/thick-shell "giant" quantum dots (gQDs) possessing type II electronic structures exhibit suppressed blinking and diminished nonradiative Auger recombination. Here we investigate CdSe/ZnSe and ZnSe/CdS as potential new gQDs. We show theoretically and experimentally that both can exhibit partial or complete spatial separation of an excited-state electron–hole pair (i.e., type II behavior). However, we reveal that thick-shell growth is challenged by competing processes: alloying and cation exchange. We demonstrate that these can be largely avoided by choice of shelling conditions (e.g., time, temperature, and QD core identity). The resulting CdSe/ZnSe gQDs exhibit unusual single-QD properties, principally emitting from dim gray statesmore » but having high two-exciton (biexciton) emission efficiencies, whereas ZnSe/CdS gQDs show characteristic gQD blinking suppression, though only if shelling is accompanied by partial cation exchange.« less

Diel plant water use and competitive soil cation exchange interact to enhance NH 4 + and K + availability in the rhizosphere

DOE PAGES

Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich; ...

2016-11-12

Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE PAGES

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer; ...

2018-04-18

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

Experimental characterization and modelization of ion exchange kinetics for a carboxylic resin in infinite solution volume conditions. Application to monovalent-trivalent cations exchange.

PubMed

Picart, Sébastien; Ramière, Isabelle; Mokhtari, Hamid; Jobelin, Isabelle

2010-09-02

This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelized by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model.

Controlling the actuation properties of MXene paper electrodes upon cation intercalation

DOE PAGES

Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; ...

2015-08-05

Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performancemore » and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.« less

Role of interlayer hydration in lincomycin sorption by smectite clays.

PubMed

Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

2009-08-15

Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

Continuous desalting of refolded protein solution improves capturing in ion exchange chromatography: A seamless process.

PubMed

Walch, Nicole; Jungbauer, Alois

2017-06-01

Truly continuous biomanufacturing processes enable an uninterrupted feed stream throughout the whole production without the need for holding tanks. We have utilized microporous anion and cation exchangers into which only salts, but not proteins, can penetrate into the pores for desalting of protein solutions, while diafiltration or dilution is usually employed for feed adjustments. Anion exchange and cation exchange chromatography columns were connected in series to remove both anions and cations. To increase operation performance, a continuous process was developed comprised of four columns. Continuous mode was achieved by staggered cycle operation, where one set of columns, consisting of one anion exchange and one cation exchange column, was loaded during the regeneration of the second set. Refolding, desalting and subsequent ion exchange capturing with a scFv as the model protein was demonstrated. The refolding solution was successfully desalted resulting in a consistent conductivity below 0.5 mS/cm from initial values of 10 to 11 mS/cm. With continuous operation process time could be reduced by 39% while productivity was increased to 163% compared to batch operation. Desalting of the protein solution resulted in up to 7-fold higher binding capacities in the subsequent ion exchange capture step with conventional protein binding resins. © 2017 The Authors. Biotechnology Journal published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Qualitative analysis scheme based on the properties of ion exchangers (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Machiroux, R.; Merciny, E.; Schreiber, A.

1973-01-01

A systematic scheme of qualitative analysis of some cations is presented. For didactic purposes the properties of cationic and anionic ion exchangers were used. At the present time, this scheme is limited to 23 ions, including Sr. (auth)

Sorption behavior of tetracyclines on suspended organic matters originating from swine wastewater.

PubMed

Lou, Yaoyin; Ye, Zhi-Long; Chen, Shaohua; Ye, Xin; Deng, Yujun; Zhang, Jianqiao

2018-03-01

Tetracyclines (TCs) discharged from livestock wastewater have aroused public concerns due to their pharmacological threats to ecosystems and human health. As an important medium in the wastewater, suspended organic matters (SOMs) play vital roles in antibiotics transport and degradation. However, limited information has been reported in the relevant literature. This study investigated TCs sorption behavior on SOM, withdrawn from swine wastewater. High TCs sorption capacities were detected, with the maximum values ranging from 0.337 to 0.679mg/g. Increasing pH and temperature led to the decline of sorption capacity. Results from three-dimensional excitation-emission matrix fluorescence spectroscopy and Fourier transform infrared spectrometry revealed that amide and carboxyl groups were the main functional groups for TCs adsorption. The interactions between SOM and TCs were clarified as predominated by hydrogen-bonding and cation-exchange in acid conditions, and electrostatic repulsion in neutral or alkaline conditions. Adsorption kinetics modeling was conducted, and a satisfactory fitting was achieved with the Freundlich equation. These results indicated that the adsorption process was a rather complex process, involving a combination of cation-exchange and hydrogen-bonding. The results will provide a better understanding of the capability of SOM for TCs transport and abatement in the wastewater treatment process. Copyright © 2017. Published by Elsevier B.V.

A Coupled THMC model of FEBEX mock-up test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Liange; Samper, Javier

2008-09-15

FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project for the engineered barrier system (EBS) of a radioactive waste repository in granite. It includes two full-scale heating and hydration tests: the in situ test performed at Grimsel (Switzerland) and a mock-up test operating at CIEMAT facilities in Madrid (Spain). The mock-up test provides valuable insight on thermal, hydrodynamic, mechanical and chemical (THMC) behavior of EBS because its hydration is controlled better than that of in situ test in which the buffer is saturated with water from the surrounding granitic rock. Here we present a coupled THMC model ofmore » the mock-up test which accounts for thermal and chemical osmosis and bentonite swelling with a state-surface approach. The THMC model reproduces measured temperature and cumulative water inflow data. It fits also relative humidity data at the outer part of the buffer, but underestimates relative humidities near the heater. Dilution due to hydration and evaporation near the heater are the main processes controlling the concentration of conservative species while surface complexation, mineral dissolution/precipitation and cation exchanges affect significantly reactive species as well. Results of sensitivity analyses to chemical processes show that pH is mostly controlled by surface complexation while dissolved cations concentrations are controlled by cation exchange reactions.« less

Localization of cesium on montmorillonite surface investigated by frequency modulation atomic force microscopy

NASA Astrophysics Data System (ADS)

Araki, Yuki; Satoh, Hisao; Okumura, Masahiko; Onishi, Hiroshi

2017-11-01

Cation exchange of clay mineral is typically analyzed without microscopic study of the clay surfaces. In order to reveal the distribution of exchangeable cations at the clay surface, we performed in situ atomic-scale observations of the surface changes in Na-rich montmorillonite due to exchange with Cs cations using frequency modulation atomic force microscopy (FM-AFM). Lines of protrusion were observed on the surface in aqueous CsCl solution. The amount of Cs of the montmorillonite particles analyzed by energy dispersive X-ray spectrometry was consistent with the ratio of the number of linear protrusions to all protrusions in the FM-AFM images. The results showed that the protrusions represent adsorbed Cs cations. The images indicated that Cs cations at the surface were immobile, and their occupancy remained constant at 10% of the cation sites at the surface with different immersion times in the CsCl solution. This suggests that the mobility and the number of Cs cations at the surface are controlled by the permanent charge of montmorillonite; however, the Cs distribution at the surface is independent of the charge distribution of the inner silicate layer. Our atomic-scale observations demonstrate that surface cations are distributed in different ways in montmorillonite and mica.

Thermochemical Stability Study of Alkyl-Tethered Quaternary Ammonium Cations for Anion Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohanty, Angela D.; Tignor, Steven E.; Sturgeon, Matthew R.

2017-01-01

The increased interest in the use of anion exchange membranes (AEMs) for applications in electrochemical devices has prompted significant efforts in designing materials with robust stability in alkaline media. Most reported AEMs suffer from polymer backbone degradation as well as cation functional group degradation. In this report, we provide comprehensive experimental investigations for the analysis of cation functional group stability under alkaline media. A silver oxide-mediated ion exchange method and an accelerated stability test in aqueous KOH solutions at elevated temperatures using a Parr reactor were used to evaluate a broad scope of quaternary ammonium (QA) cationic model compound structures,more » particularly focusing on alkyl-tethered cations. Additionally, byproduct analysis was employed to gain better understanding of degradation pathways and trends of alkaline stability. Experimental results under different conditions gave consistent trends in the order of cation stability of various QA small molecule model compounds. Overall, cations that are benzyl-substituted or that are near to electronegative atoms (such as oxygen) degrade faster in alkaline media in comparison to alkyl-tethered QAs. These comprehensive model compound stability studies provide valuable information regarding the relative stability of various cation structures and can help guide researchers towards designing new and promising candidates for AEM materials.« less

Coping with effects of high dissolved salt samples on the inductively coupled plasma spectrometer

Treesearch

Jane E. Hislop; James W. Hornbeck; James W. Hornbeck

2002-01-01

Research on acidic forest soils typically uses unbuffered salt solutions as extractants for exchangeable cations. Our lab uses 1 M NH4C1 extractant for exchangeable cations (Ca, K, Mg, and Na) and 1 M KC1 for exchangeable aluminum. The resulting high dissolved salt solutions presented chronic analytical problems on flame atomic absorption spectrophotometer (AAS) and...

Solid-phase extraction sorbent consisting of alkyltrimethylammonium surfactants immobilized onto strong cation-exchange polystyrene resin.

PubMed

Reid, Kendra R; Kennedy, Lonnie J; Crick, Eric W; Conte, Eric D

2002-10-25

Presented is a solid-phase extraction sorbent material composed of cationic alkyltrimethylammonium surfactants attached to a strong cation-exchange resin via ion-exchange. The original hydrophilic cation-exchange resin is made hydrophobic by covering the surface with alkyl chains from the hydrophobic portion of the surfactant. The sorbent material now has a better ability to extract hydrophobic molecules from aqueous samples. The entire stationary phase (alkyltrimethylammonium surfactant) is removed along with the analyte during the elution step. The elution step requires a mild elution solvent consisting of 0.25 M Mg2+ in a 50% 2-propanol solution. The main advantage of using a removable stationary phase is that traditionally utilized toxic elution solvents such as methylene chloride, which are necessary to efficiently release strongly hydrophobic species from SPE stationary phases, may now be avoided. Also, the final extract is directly compatible with reversed-phase liquid chromatography. The performance of this procedure is presented using pyrene as a test molecule.

Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts

PubMed Central

Bhaskar, M.; Surekha, M.; Suma, N.

2018-01-01

The liquid phase esterification of phenyl acetic acid with p-cresol over different metal cation exchanged montmorillonite nanoclays yields p-cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (Mn+ = Al3+, Zn2+, Mn2+, Fe3+, Cu2+) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al3+-montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p-cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1H NMR and 13C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation. PMID:29515855

Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Burns, Peter C., E-mail: pburns@nd.edu; Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556

2014-05-01

The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are amore » framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild hydrothermal treatments. The framework of these compounds is robust to cation exchange and heat. (yellow polyhedra=uranium pentagonal bipyramids; blue polyhedra=tungsten octahedral, purple balls=K; yellow balls=Na; grey balls=Tl). - Highlights: • Five isostructural uranyl tungstates compounds were synthesized hydrothermally. • The structures consist of a chains of uranium and tungstate polyhedral. • Chains are connected into a framework by cation–cation interactions. • Cation exchange does not alter the structural integrity of the compounds. • Cation exchange was successful at room temperature and mild hydrothermal conditions.« less

Applications for special-purpose minerals at a lunar base

NASA Technical Reports Server (NTRS)

Ming, Douglas W.

1992-01-01

Maintaining a colony on the Moon will require the use of lunar resources to reduce the number of launches necessary to transport goods from the Earth. It may be possible to alter lunar materials to produce minerals or other materials that can be used for applications in life support systems at a lunar base. For example, mild hydrothermal alteration of lunar basaltic glasses can produce special-purpose minerals (e.g., zeolites, smectites, and tobermorites) that in turn may be used in life support, construction, waste renovation, and chemical processes. Zeolites, smectites, and tobermorites have a number of potential applications at a lunar base. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations that possess infinite, three-dimensional crystal structures. They are further characterized by an ability to hydrate and dehydrate reversibly and to exchange some of their constituent cations, both without major change of structure. Based on their unique absorption, cation exchange, molecular sieving, and catalytic properties, zeolites may be used as a solid support medium for the growth of plants, as an adsorption medium for separation of various gases (e.g., N2 from O2), as catalysts, as molecular sieves, and as a cation exchanger in sewage-effluent treatment, in radioactive waste disposal, and in pollution control. Smectites are crystalline, hydrated 2:1 layered aluminosilicates that also have the ability to exchange some of their constituent cations. Like zeolites, smectites may be used as an adsorption medium for waste renovation, as adsorption sites for important essential plant growth cations in solid support plant growth mediums (i.e., 'soils'), as cation exchangers, and in other important application. Tobermorites are cystalline, hydrated single-chained layered silicates that have cation-exchange and selectivity properties between those of smectites and most zeolites. Tobermorites may be used as a cement in building lunar base structures, as catalysts, as media for nuclear and hazardous waste disposal, as exchange media for waste-water treatment, and in other potential applications. Special-purpose minerals synthesized at a lunar base may also have important applications at a space station and for other planetary missions. New technologies will be required at a lunar base to develop life support systems that are self-sufficient, and the use of special-purpose minerals may help achieve this self-sufficiency.

Ionic Control of the Reversal Response of Cilia in Paramecium caudatum

PubMed Central

Naitoh, Yutaka

1968-01-01

The duration of ciliary reversal of Paramecium caudatum in response to changes in external ionic factors was determined with various ionic compositions of both equilibration and stimulation media. The reversal response was found to occur when calcium ions bound by an inferred cellular cation exchange system were liberated in exchange for externally applied cations other than calcium. Factors which affect the duration of the response were (a) initial amount of calcium bound by the cation exchange system, (b) final amount of calcium bound by the system after equilibration with the stimulation medium, and (c) concentration of calcium ions in the stimulation medium. An empirical equation is presented which relates the duration of the response to these three factors. On the basis of these and previously published data, the following hypothesis is proposed for the mechanism underlying ciliary reversal in response to cationic stimulation: Ca++ liberated from the cellular cation exchange system activates a contractile system which is energized by ATP. Contraction of this component results in the reversal of effective beat direction of cilia by a mechanism not yet understood. The duration of reversal in live paramecia is related to the time course of bound calcium release. PMID:4966766

On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution.

PubMed

Prelot, Benedicte; Ayed, Imen; Marchandeau, Franck; Zajac, Jerzy

2014-01-01

Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium. Compared to the retention limits of both resins under such idealized conditions, an important depression in the maximum adsorption capacity toward each main component was observed in multication systems. The overall effect of ion exchange process appeared to be an unpredictable outcome of the individual sorption capacities of the two resins toward various cations as a function of the cation charge, size, and concentration. The cesium retention capacity of the resins was diminished to about 25% of the "ideal" value in Effluent 1 and 50% in Effluent 2; a further decrease to about 15% was observed upon concomitant strontium addition. The uptake of strontium by the resins was found to be less sensitive to the addition of other metal components: the greatest decrease in the amount adsorbed was 60% of the ideal value in the two effluents for Amberlite® IRN77 and 75% for Amberlite™ IRN9652. It was therefore demonstrated that any performance tests carried out under idealized conditions should be exploited with much caution to predict the real performance of cation exchange resins under conditions of cation competition.

Niobate-based octahedral molecular sieves

DOEpatents

Nenoff, Tina M.; Nyman, May D.

2006-10-17

Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

Niobate-based octahedral molecular sieves

DOEpatents

Nenoff, Tina M.; Nyman, May D.

2003-07-22

Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

ABSORPTION METHOD FOR SEPARATING METAL CATIONS

DOEpatents

Tompkins, E.R.; Parker, G.W.

1959-03-10

An improved method is presented for the chromatographic separation of fission products wherein a substantial reduction in liquid volume is obtained. The process consists in contacting a solution containing fission products with a body of ion-exchange adsorbent to effect adsorption of fission product cations. The loaded exchange resin is then contacted with a small volume of a carboxylic acid eluant, thereby recovering the fission products. The fission product carrying eluate is acidified without increasing its volume to the volume of the original solution, and the acidified eluate is then used as a feed solution for a smaller body of ion-exchange resin effecting readsorption of the fission product cations.

Mechanism of epithelial lithium transport. Evidence for basolateral Na:Na and Na:Li exchange

PubMed Central

1983-01-01

Measurement of transmural sodium fluxes across isolated, ouabain- inhibited turtle colon in the presence of a serosal-to-mucosal sodium gradient shows that in the absence of active transport the amiloride- sensitive cellular path contains at least two routes for the transmural movement of sodium and lithium, one a conductive path and the other a nonconductive, cation-exchange mechanism. The latter transport element can exchange lithium for sodium, and the countertransport of these two cations provides a mechanistic basis for the ability of tight epithelia to actively absorb lithium despite the low affinity of the basolateral Na/K-ATPase for this cation. PMID:6644269

Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction.

PubMed

Ma, Heping; Liu, Bailing; Li, Bin; Zhang, Liming; Li, Yang-Guang; Tan, Hua-Qiao; Zang, Hong-Ying; Zhu, Guangshan

2016-05-11

Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials.

Humic Acid Isolations from Lignite by Ion Exchange Method

NASA Astrophysics Data System (ADS)

Kurniati, E.; Muljani, S.; Virgani, D. G.; Neno, B. P.

2018-01-01

The humic liquid is produced from lignite extraction using alkali solution. Conventional humic acid is obtained by acidifying a humic solution using HCl. The purpose of this research is the formation of solid humic acid from lignite by ion exchange method using cation resin. The results showed that the addition of cation resin was able to reduce the pH from 14 to pH 2 as well as the addition of acid (HCl), indicating the exchange of Na + ions with H + ions. The reduction of pH in the humic solution is influenced by the concentration of sodium ions in the humic solution, the weight of the cation resin, and the ion exchange time. The IR spectra results are in good agreement for humic acid from lignite characterization.

Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

PubMed

Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

2017-11-07

Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

Influence of acetazolamide loading on the (in vitro) performances of non-phospholipid-based cationic nanosized emulsion in comparison with phospholipid-based anionic and neutral-charged nanosized emulsions.

PubMed

Tamilvanan, Shunmugaperumal; Kumar, Balakrishnan Ajith

2011-09-01

Acetazolamide (ACZM)-loaded anionic, cationic, and neutral-charged oil-in-water nanosized emulsions were prepared and compared with their mean droplet diameter, surface charge, entrapment efficiency, freeze-thaw cycling stability, in vitro drug release, and transcorneal permeation. The present study aims to determine the influence of ACZM loading on the performances of non-phospholipid-based cationic nanosized emulsion in comparison with phospholipid-based anionic and neutral-charged nanosized emulsions. Regardless of charges, all of these emulsions exhibited a nanometer range mean particle diameter (240-443 nm) following autoclave sterilization. While the anionic and cationic emulsions did show high negative (-36.9 mV) and positive zeta potential (+41.4 mV) values, the neutral-charged emulsion did not. Presence of cryoprotectants (5% w/w sucrose + 5% w/w sorbitol) improved the stability of cationic emulsion to droplet aggregation during freeze-thaw cycling. The in vitro release kinetic behavior of drug exchange with physiological anions present in the simulated tear solution appears to be complex and difficult to characterize using mathematical fitting model equations. Augmentation in drug permeation through goat cornea, in vitro, was noticed for cationic emulsion. ACZM-loaded cationic nanosized emulsion could be suitable for topical application into eye to elicit better therapeutic effect in comparison with its anionic and neutral-charged emulsions.

Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area.

PubMed Central

Lipson, S M; Stotzky, G

1983-01-01

The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the added virus population was adsorbed, regardless of the concentration of infectious particles. A heterogeneity within the reovirus population was indicated. PMID:6639022

Study of Np(V) Sorption by Ionic Exchange on Na, K, Ca and Mg-Montmorillonite

NASA Astrophysics Data System (ADS)

Benedicto, A.; Begg, J.; Zhao, P.; Kersting, A. B.; Zavarin, M.

2012-12-01

The transport behavior of actinides in soil and ground water are highly influenced by clay minerals due to their ubiquity in the environment, reactivity and colloidal properties. Neptunium(V) has been introduced in the environment as a result of nuclear weapons testing [e.g. 1, 2] and is a radionuclide of potential interest for safety assessment of high level radioactive waste disposal because its long half-life and high toxicity [3]. Surface complexation and ionic exchange have been identified as Np(V) sorption mechanisms onto montmorillonite. At pH below 5, Np(V) sorption is mainly attributed to ionic exchange. This study examines Np(V) ion exchange on Na, K, Ca and Mg forms of montmorillonite. Experiments were carried out using 237Np concentrations between 2 x 10-8 M and 5 x 10-6 M at three different ionic strengths 0.1, 0.01 and 0.001M. The pH was maintained at 4.5. Np(V) sorption to montmorillonite homoionized with monovalent cations (Na and K) demonstrated a markedly different behavior to that observed for montmorillonite homoionized with divalent cations (Ca and Mg). Np sorption to Na and K-montmorillonite was greater than Np sorption to Ca and Mg-montmorillonite. Isotherms with Na and K-montmorillonite showed a strong dependence on ionic strength: the percentage of Np adsorbed was near zero at 0.1M ionic strength, but increased to 30% at 0.001 M ionic strength. This suggests ionic exchange is the main Np adsorption mechanism under the experimental conditions investigated. Dependence on ionic strength was not observed in the Np sorption isotherms for Ca and Mg-montmorillonite indicating a low exchange capacity between Np and divalent cations. Modeling of the sorption experimental data will allow determination of the Na+↔NpO2+ and K+↔NpO2+ ionic exchange constants on montmorillonite. References: [1] A. R. Felmy; K. J. Cantrell; S. D. Conradson, Phys. Chem. Earth 2010, 35, 292-297 [2] D. K. Smith; D. L. Finnegan; S. M. Bowen, J. Environ. Radioact. 2003, 67, (1), 35-51 [3] N. Kozai; T. Ohnuki; S. Muraoka, J. Nucl. Sci. Technol. 1993, 30, (11), 1153-1159 This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. A. Benedicto was supported by a Spanish Ministry of Science and Innovation 'FPI' pre-doctoral contract in CIEMAT (Spain). LLNL-ABS-570160

The use of laboratory-determined ion exchange parameters in the predictive modelling of field-scale major cation migration in groundwater over a 40-year period.

PubMed

Carlyle, Harriet F; Tellam, John H; Parker, Karen E

2004-01-01

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na(+), K(+), Ca(2+), and Mg(2+) were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in approximately 1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO(3) and pH values. However, by including partial CO(2) degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO(4), HCO(3), and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.

The use of laboratory-determined ion exchange parameters in the predictive modelling of field-scale major cation migration in groundwater over a 40-year period

NASA Astrophysics Data System (ADS)

Carlyle, Harriet F.; Tellam, John H.; Parker, Karen E.

2004-01-01

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na +, K +, Ca 2+, and Mg 2+ were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in ˜1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO 3 and pH values. However, by including partial CO 2 degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO 4, HCO 3, and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.

High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

PubMed

Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

2018-04-11

The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

Na, K, Rb, and Cs Exchange in Heulandite Single-Crystals: X-Ray Structure Refinements at 100 K

NASA Astrophysics Data System (ADS)

Yang, Ping; Armbruster, Thomas

1996-04-01

The crystal structures of Na-, K-, Rb-, and Cs-exchanged varieties of the zeolite heulandite with the simplified compositionM+9Al9Si27O72·nH2O were studied by single-crystal X-ray diffraction at 100 K. The structure refinements of Na-, K-, and Rb-exchanged heulandite were performed in space groupC2/mwith resultantRvalues of 3.8, 3.0, and 4.9%, respectively. Cs-exchanged heulandite was refined in space groupC[formula], yielding anRvalue of 3.4%. X-ray single-crystal data of the Cs-exchanged variety indicated that many reflections of typeh k lwere not equivalent toh -k las expected for monoclinic symmetry. With increasing radius of the incorporated channel cations, thebaxis increases from 17.93 to 18.09 Å leading to a slight widening of the channels. The number of H2O molecules also decreases with increasing cation radius due to space limitations. Three general cation positions (II-1,C3, andB4) were found in the four exchanged heulandite samples. For Rb- and Cs-exchanged crystals, the additional cation siteA2 occurs. In Cs-exchanged heulandite symmetry lowering is due to partial Si, Al ordering in the framework accompanied with a more asymmetric arrangement of channel Cs. Only if heavy elements in the channels are present the symmetry information of the framework is enforced, thus partial Si, Al ordering can be resolved.

Magnetic relaxation of 1D coordination polymers (X)₂[Mn(acacen)Fe(CN)₆], X = Ph₄P⁺, Et₄N⁺.

PubMed

Rams, Michał; Peresypkina, Eugenia V; Mironov, Vladimir S; Wernsdorfer, Wolfgang; Vostrikova, Kira E

2014-10-06

Substitution of the organic cation X in the 1D polymer, (X)2[Mn(acacen)Fe(CN)6], leads to an essential change in magnetic behavior. Due to the presence of more voluminous Ph4P(+) cations, the polyanion has a more geometrically distorted chain skeleton and, as a consequence, enhanced single chain magnet (SCM) characteristics compared to those for Et4N(+). The Arrhenius relaxation energy barriers, the exchange interaction constant and the zero-field splitting anisotropy of Mn(III) are determined from the analysis of magnetic measurements. The discussion is supported with ligand field calculations for [Fe(CN)6](3-) that unveils the significant anisotropy of Fe magnetic moments.

Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

PubMed

Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

2011-10-01

The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Diazonium cation-exchanged clay: an efficient, unfrequented route for making clay/polymer nanocomposites.

PubMed

Salmi, Zakaria; Benzarti, Karim; Chehimi, Mohamed M

2013-11-05

We describe a simple, off-the-beaten-path strategy for making clay/polymer nanocomposites through tandem diazonium salt interface chemistry and radical photopolymerization. Prior to photopolymerization, sodium montmorillonite (MMT) was ion exchanged with N,N'-dimethylbenzenediazonium cation (DMA) from the tetrafluoroborate salt precursor. DMA acts as a hydrogen donor for benzophenone in solution; this pair of co-initiators permits us to photopolymerize glycidyl methacrylate (GMA) between the lamellae of the diazonium-modified clay, therefore providing intercalated MMT-PGMA nanocomposites with an onset of exfoliation. This work conclusively provides a new approach for bridging reactive and functional polymers to layered nanomaterials via aryl diazonium salts in a simple, fast, efficient cation-exchange approach.

Properties and applications of zeolites.

PubMed

Rhodes, Christopher J

2010-01-01

Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix.

The ins and outs of intracellular ion homeostasis: NHX-type cation/H(+) transporters.

PubMed

Bassil, Elias; Blumwald, Eduardo

2014-12-01

The biochemical characterization of cation/H(+) exchange has been known since 1985 [1], yet only recently have we begun to understand the contribution of individual exchangers to ion homeostasis in plants. One particularly important class of exchangers is the NHX-type that is associated with Na(+) transport and therefore salinity tolerance. New evidence suggests that under normal growth conditions NHXs are critical regulators of K(+) and pH homeostasis and have important roles, depending on their cellular localization, in the generation of turgor as well as in vesicular trafficking. Recent advances highlight novel and exciting functions of intracellular NHXs in growth and development, stress adaptation and osmotic adjustment. Here, we elaborate on new and emerging cellular and physiological functions of this group of H(+)-coupled cation exchangers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mesoporous titanium phosphate molecular sieves with ion-exchange capacity.

PubMed

Bhaumik, A; Inagaki, S

2001-01-31

Novel open framework molecular sieves, titanium(IV) phosphates named, i.e., TCM-7 and -8 (Toyota Composite Materials, numbers 7 and 8), with new mesoporous cationic framework topologies obtained by using both cationic and anionic surfactants are reported. The (31)P MAS NMR, UV-visible absorption, and XANES data suggest the tetrahedral state of P and Ti, and stabilization of the tetrahedral state of Ti in TCM-7/8 is due to the incorporation of phosphorus (at Ti/P = 1:1) vis-à-vis the most stable octahedral state of Ti in the pure mesoporous TiO(2). Mesoporous TCM-7 and -8 show anion exchange capacity due to the framework phosphonium cation and cation exchange capacity due to defective P-OH groups. The high catalytic activity in the liquid-phase partial oxidation of cyclohexene with a dilute H(2)O(2) oxidant supports the tetrahedral coordination of Ti in these materials.

Restructuring of a Peat in Interaction with Multivalent Cations: Effect of Cation Type and Aging Time

PubMed Central

Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J. A.; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

2013-01-01

It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al3+, Ca2+ or Na+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation. PMID:23750256

Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

PubMed

Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

2013-01-01

It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

In vivo cation exchange in quantum dots for tumor-specific imaging.

PubMed

Liu, Xiangyou; Braun, Gary B; Qin, Mingde; Ruoslahti, Erkki; Sugahara, Kazuki N

2017-08-24

In vivo tumor imaging with nanoprobes suffers from poor tumor specificity. Here, we introduce a nanosystem, which allows selective background quenching to gain exceptionally tumor-specific signals. The system uses near-infrared quantum dots and a membrane-impermeable etchant, which serves as a cation donor. The etchant rapidly quenches the quantum dots through cation exchange (ionic etching), and facilitates renal clearance of metal ions released from the quantum dots. The quantum dots are intravenously delivered into orthotopic breast and pancreas tumors in mice by using the tumor-penetrating iRGD peptide. Subsequent etching quenches excess quantum dots, leaving a highly tumor-specific signal provided by the intact quantum dots remaining in the extravascular tumor cells and fibroblasts. No toxicity is noted. The system also facilitates the detection of peritoneal tumors with high specificity upon intraperitoneal tumor targeting and selective etching of excess untargeted quantum dots. In vivo cation exchange may be a promising strategy to enhance specificity of tumor imaging.The imaging of tumors in vivo using nanoprobes has been challenging due to the lack of sufficient tumor specificity. Here, the authors develop a tumor-specific quantum dot system that permits in vivo cation exchange to achieve selective background quenching and high tumor-specific imaging.

A method for the production of weakly acidic cation exchange resins

NASA Astrophysics Data System (ADS)

Heller, H.; Werner, F.; Mitschker, A.; Diehl, H. V.; Schaefer, A.

1991-12-01

The invention relates to a nonpolluting method for the production of weakly acidic cation exchange resins by saponification of cross-linked acrylonitrile bead polymers, with an alkaline saponification agent at elevated temperature, according to which method the bead polymer and alkaline saponification agent are jointly added only at elevated temperature.

Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

PubMed Central

Šljukić, Biljana; Morais, Ana L.; Santos, Diogo M. F.; Sequeira, César A. C.

2012-01-01

Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC’s performance. Cell polarization, power density, stability, and durability tests are used in the membranes’ evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load. PMID:24958292

Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

PubMed

Sljukić, Biljana; Morais, Ana L; Santos, Diogo M F; Sequeira, César A C

2012-07-19

Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC's performance. Cell polarization, power density, stability, and durability tests are used in the membranes' evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load.

Protein Phylogenetic Analysis of Ca2+/cation Antiporters and Insights into their Evolution in Plants

PubMed Central

Emery, Laura; Whelan, Simon; Hirschi, Kendal D.; Pittman, Jon K.

2012-01-01

Cation transport is a critical process in all organisms and is essential for mineral nutrition, ion stress tolerance, and signal transduction. Transporters that are members of the Ca2+/cation antiporter (CaCA) superfamily are involved in the transport of Ca2+ and/or other cations using the counter exchange of another ion such as H+ or Na+. The CaCA superfamily has been previously divided into five transporter families: the YRBG, Na+/Ca2+ exchanger (NCX), Na+/Ca2+, K+ exchanger (NCKX), H+/cation exchanger (CAX), and cation/Ca2+ exchanger (CCX) families, which include the well-characterized NCX and CAX transporters. To examine the evolution of CaCA transporters within higher plants and the green plant lineage, CaCA genes were identified from the genomes of sequenced flowering plants, a bryophyte, lycophyte, and freshwater and marine algae, and compared with those from non-plant species. We found evidence of the expansion and increased diversity of flowering plant genes within the CAX and CCX families. Genes related to the NCX family are present in land plant though they encode distinct MHX homologs which probably have an altered transport function. In contrast, the NCX and NCKX genes which are absent in land plants have been retained in many species of algae, especially the marine algae, indicating that these organisms may share “animal-like” characteristics of Ca2+ homeostasis and signaling. A group of genes encoding novel CAX-like proteins containing an EF-hand domain were identified from plants and selected algae but appeared to be lacking in any other species. Lack of functional data for most of the CaCA proteins make it impossible to reliably predict substrate specificity and function for many of the groups or individual proteins. The abundance and diversity of CaCA genes throughout all branches of life indicates the importance of this class of cation transporter, and that many transporters with novel functions are waiting to be discovered. PMID:22645563

Evaluation of soils for use as liner materials: a soil chemistry approach.

PubMed

DeSutter, Tom M; Pierzynski, Gary M

2005-01-01

Movement of NH(4)(+) below animal waste lagoons is generally a function of the whole-lagoon seepage rate, soil mineralogy, cations in the lagoon liquor, and selectivity for NH(4)(+) on the soil-exchange sites. Binary exchange reactions (Ca(2+)-K(+), Ca(2+)-NH(4)(+), and K(+)-NH(4)(+)) were conducted on two soils from the Great Plains and with combinations of these soils with bentonite or zeolite added. Binary exchanges were used to predict ternary exchanges Ca(2+)-K(+)-NH(4)(+) following the Rothmund-Kornfeld approach and Gaines-Thomas convention. Potassium and NH(4)(+) were preferred over Ca(2+), and K(+) was preferred over NH(4)(+) in all soils and soils with amendments. Generally, the addition of bentonite did not change cation selectivity over the native soils, whereas the addition of zeolite did. The Rothmund-Kornfeld approach worked well for predicting equivalent fractions of cations on the exchanger phase when only ternary-solution phase compositions were known. Actual swine- and cattle-lagoon solution compositions and the Rothmund-Kornfeld approach were used to project that native soils are predicted to retain 53 and 23%, respectively, of the downward-moving NH(4)(+) on their exchange sites. Additions of bentonite or zeolite to soils under swine lagoons may only slightly improve the equivalent fraction of NH(4)(+) on the exchange sites. Although additions of bentonite or zeolite may not help increase the NH(4)(+) selectivity of a liner material, increases in the overall cation exchange capacity (CEC) of a soil will ultimately decrease the amount of soil needed to adsorb downward-moving NH(4)(+).

Model simulations of a field experiment on cation exchange-affected multicomponent solute transport in a sandy aquifer

NASA Astrophysics Data System (ADS)

Bjerg, Poul L.; Ammentorp, Hans C.; Christensen, Thomas H.

1993-04-01

A large-scale and long-term field experiment on cation exchange in a sandy aquifer has been modelled by a three-dimensional geochemical transport model. The geochemical model includes cation-exchange processes using a Gaines-Thomas expression, the closed carbonate system and the effects of ionic strength. Information on geology, hydrogeology and the transient conservative solute transport behaviour was obtained from a dispersion study in the same aquifer. The geochemical input parameters were carefully examined. CEC and selectivity coefficients were determined on the actual aquifer material by batch experiments and by the composition of the cations on the exchange complex. Potassium showed a non-ideal exchange behaviour with KCa selectivity coefficients indicating dependency on equivalent fraction and K + concentration in the aqueous phase. The model simulations over a distance of 35 m and a period of 250 days described accurately the observed attenuation of Na and the expelled amounts of Ca and Mg. Also, model predictions of plateau zones, formed by interaction with the background groundwater, in general agreed satisfactorily with the observations. Transport of K was simulated over a period of 800 days due to a substantially attenuation in the aquifer. The observed and the predicted breakthrough curves showed a reasonable accordance taking the duration of the experiment into account. However, some discrepancies were observed probably caused by the revealed non-ideal exchange behaviour of K +.

On the influence of ion exchange on the local structure of the titanosilicate ETS-10.

PubMed

Pavel, Claudiu C; Zibrowius, Bodo; Löffler, Elke; Schmidt, Wolfgang

2007-07-14

The effect of ion exchange with different monovalent cations (NH(4)(+), K(+), Na(+) and Cs(+)) on the local structure of the titanosilicate ETS-10 has been studied by (29)Si MAS NMR and Raman spectroscopy. Although X-ray diffraction shows no significant influence of ion exchange on the long range order, ammonium exchange is found to result in substantial damage to the local structure. Ion exchange experiments with alkali cations under significantly more acidic conditions clearly show that the structural damage brought about by ammonium exchange is not caused by the low pH of the exchange solution. The exchange with potassium and caesium ions also leads to significant changes in the (29)Si NMR and Raman spectra. However, these changes can largely be reversed by sodium back-exchange.

Effects of Cationic Pendant Groups on Ionic Conductivity for Anion Exchange Membranes: Structure Conductivity Relationships

NASA Astrophysics Data System (ADS)

Kim, Sojeong; Choi, Soo-Hyung; Lee, Won Bo

Anion exchange membranes(AEMs) have been widely studied due to their various applications, especially for Fuel cells. Previous proton exchange membranes(PEMs), such as Nafions® have better conductivity than AEMs so far. However, technical limitations such as slow electrode kinetics, carbon monoxide (CO) poisoning of metal catalysts, high methanol crossover and high cost of Pt-based catalyst detered further usages. AEMs have advantages to supplement its drawbacks. AEMs are environmentally friendly and cost-efficient. Based on the well-defined block copolymer, self-assembled morphology is expected to have some relationship with its ionic conductivity. Recently AEMs based on various cations, including ammonium, phosphonium, guanidinium, imidazolium, metal cation, and benzimidazolium cations have been developed and extensively studied with the aim to prepare high- performance AEMs. But more fundamental approach, such as relationships between nanostructure and conductivity is needed. We use well-defined block copolymer Poly(styrene-block-isoprene) as a backbone which is synthesized by anionic polymerization. Then we graft various cationic functional groups and analysis the relation between morphology and conductivity. Theoretical and computational soft matter lab.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

PubMed Central

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.

2017-01-01

Ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)–water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface. PMID:28598428

Impact of soil properties on selected pharmaceuticals adsorption in soils

NASA Astrophysics Data System (ADS)

Kodesova, Radka; Kocarek, Martin; Klement, Ales; Fer, Miroslav; Golovko, Oksana; Grabic, Roman; Jaksik, Ondrej

2014-05-01

The presence of human and veterinary pharmaceuticals in the environment has been recognized as a potential threat. Pharmaceuticals may contaminate soils and consequently surface and groundwater. Study was therefore focused on the evaluation of selected pharmaceuticals adsorption in soils, as one of the parameters, which are necessary to know when assessing contaminant transport in soils. The goals of this study were: (1) to select representative soils of the Czech Republic and to measure soil physical and chemical properties; (2) to measure adsorption isotherms of selected pharmaceuticals; (3) to evaluate impact of soil properties on pharmaceutical adsorptions and to propose pedotransfer rules for estimating adsorption coefficients from the measured soil properties. Batch sorption tests were performed for 6 selected pharmaceuticals (beta blockers Atenolol and Metoprolol, anticonvulsant Carbamazepin, and antibiotics Clarithromycin, Trimetoprim and Sulfamethoxazol) and 13 representative soils (soil samples from surface horizons of 11 different soil types and 2 substrates). The Freundlich equations were used to describe adsorption isotherms. The simple correlations between measured physical and chemical soil properties (soil particle density, soil texture, oxidable organic carbon content, CaCO3 content, pH_H2O, pH_KCl, exchangeable acidity, cation exchange capacity, hydrolytic acidity, basic cation saturation, sorption complex saturation, salinity), and the Freundlich adsorption coefficients were assessed using Pearson correlation coefficient. Then multiple-linear regressions were applied to predict the Freundlich adsorption coefficients from measured soil properties. The largest adsorption was measured for Clarithromycin (average value of 227.1) and decreased as follows: Trimetoprim (22.5), Metoprolol (9.0), Atenolol (6.6), Carbamazepin (2.7), Sulfamethoxazol (1.9). Absorption coefficients for Atenolol and Metoprolol closely correlated (R=0.85), and both were also related to absorption coefficients of Carbamazepin (R=0.67 and 0.68). Positive correlation was found between Trimetoprim absorption coefficients and Atenolol, Metoprolol or Carbamazepin absorption coefficients. The negative relationship was found between absorption coefficients of Sulfomethoxazol and Clarithromycin (R=-0.80). Sulfamethoxazol absorption coefficient was negatively related to pH_H2O, pH_KCL or sorption complex saturation and positively to the hydrolytic acidity or exchangeable acidity. Trimetoprim absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation or silt content and negatively to particle density or sand content. Clarithromycin absorption coefficient was positively related to pH_H2O, pH_KCL, CaCO3 content, basic cation saturation or sorption complex saturation and negatively to hydrolytic acidity or exchangeable acidity. Atenolol and Metoprolol absorption coefficients were positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation, salinity, clay content or silt content, and negatively to the particle density or sand content. Finally Carbamazepin absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity or basic cation saturation, and negatively to the particle density or sand content. Evaluated pedotransfer rules for different pharmaceuticals included different sets of soil properties. Absorption coefficients could be predicted from: the hydrolytic acidity (Sulfamethoxazol), the oxidable organic carbon content (Trimetoprim and Carbamazepin), the oxidable organic carbon content, hydrolytic acidity and cation exchange capacity (Clarithromycin), the basic cation saturation (Atenolol and Metoprolol). Acknowledgement: Authors acknowledge the financial support of the Czech Science Foundation (Project No. 13-12477S).

A polymeric liquid membrane electrode responsive to 3,3',5,5'-tetramethylbenzidine oxidation for sensitive peroxidase/peroxidase mimetic-based potentiometric biosensing.

PubMed

Wang, Xuewei; Yang, Yangang; Li, Long; Sun, Mingshuang; Yin, Haogen; Qin, Wei

2014-05-06

The oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) has great utility in bioanalysis such as peroxidase/peroxidase mimetic-based biosensing. In this paper, the behaviors of TMB oxidation intermediates/products in liquid/liquid biphasic systems have been investigated for the first time. The free radical, charge transfer complex, and diimine species generated by TMB oxidation are all positively charged under acidic and near-neutral conditions. Electron paramagnetic resonance and visible absorbance spectroscopy data demonstrate that these cationic species can be effectively transferred from an aqueous phase into a water-immiscible liquid phase functionalized by an appropriate cation exchanger. Accordingly, sensitive potential responses of TMB oxidation have been obtained on a cation exchanger-doped polymeric liquid membrane electrode under mildly acidic and near-neutral conditions. By using the membrane electrode responsive to TMB oxidations, two sensitive potentiometric biosensing schemes including the peroxidase-labeled sandwich immunoassay and G-quadruplex DNAzyme-based DNA hybridization assay have been developed. The obtained detection limits for the target antigen and DNA are 0.02 ng/mL and 0.1 nM, respectively. Coupled with other advantages such as low cost, high reliability, and ease of miniaturization and integration, the proposed polymeric liquid membrane electrode holds great promise as a facile and efficient transducer for TMB oxidation and related biosensing applications.

Sorption of phenol and alkylphenols from aqueous solution onto organically modified montmorillonite and applications of dual-mode sorption model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huh, J.K.; Song, D.I.; Jeon, Y.W.

2000-01-01

Single- and multisolute competitive sorptions were carried out in a batch reactor to investigate the uptake of phenol, 4-methylphenol (MeP), 2,4-dimethylphenol (DMeP), and 4-ethylphenol (EtP) dissolved in water at 25 C onto organically modified montmorillonite. Hexadecyltrimethylammonium (HDTMA) cation was exchanged for metal cations on the montmorillonite to the extent of the cation-exchange capacity (CEC) of the montmorillonite to prepare HDTMA-montmorillonite, changing its surface property from hydrophilic to organophilic. It was observed from the experimental results that the adsorption affinity on HDTMA-montmorillonite was in the order 4-EtP {approx} 2,4-DMeP > 4-MeP > phenol. The Langmuir, dual-mode sorption (DS), and Redlich-Peterson (RP)more » models were used to analyze the single-solute sorption equilibria. The competitive Langmuir model (CLM), competitive dual-mode sorption model (CDSM), and ideal adsorbed solution theory (IAST), coupled with the single-solute models (i.e., Langmuir, DS, and RP models), were used to predict the multisolute competitive sorption equilibria. All the models considered in this work yielded favorable representations of both single- and multisolute sorption behaviors. DSM, CDSM, and IAST coupled with the DSM were found to be other satisfactory models to describe the single- and multisolute sorption of the phenolic compounds onto HDTMA-montmorillonite.« less

Metal chalcogenide nanoparticle gel networks: Their formation mechanism and application for novel material generation and heavy metal water remediation via cation exchange reactions

NASA Astrophysics Data System (ADS)

Palhares, Leticia F.

The dissertation research is focused on (1) uncovering the mechanism of metal chalcogenide nanoparticle gel formation; (2) extending the cation exchange reaction protocol to zinc sulfide gel networks, with the goal of accessing new aerogel chemistries and understanding the factors that drive the process; and (3) conducting a quantitative analysis of the ability of ZnS aerogels to remove heavy metal ions from aqueous solutions. The mechanism of metal chalcogenide nanoparticle gel formation was investigated using Raman spectroscopy and X-ray Photoelectron Spectroscopy to probe the chemical changes that occur during the gelation process. These techniques suggest that the bonding between the particles in the CdSe nanoparticle gels is due to the oxidation of surface selenide species, forming covalent Se--Se bonds. Treating the gel networks with a suitable reducing agent, such as a thiol, breaks the covalent bond and disperses the gel network. The addition of sodium borohydride, a "pure" reducing agent, also breaks down the gel network, strengthening the hypothesis that the reducing character of the thiols, not their ligation ability, is responsible for the gel network breakdown. UV-Vis spectroscopy, Transmission Electron Microscopy and Powder X-ray Diffraction were used to analyze the particles after successive gelation-dispersion cycles. The primary particle size decreases after repeated oxidation-reduction cycles, due to nanoparticle surface etching. This trend is observed for CdSe and CdS gel networks, allowing for the proposition that the oxidative-reductive mechanism responsible for the formation-dispersion of the gels is general, applying to other metal chalcogenide nanocrystals as well. The cation exchange reaction previously demonstrated for CdSe gels was extended to ZnS gel networks. The exchange occurs under mild reaction conditions (room temperature, methanol solvent) with exchanging ions of different size, charge and mobility (Ag+, Pb2+, Cd2+ , Cu2+). The overall reaction is kinetically controlled, since systems with similar solubility, and thus similar thermodynamic driving force (e.g. PbS and CdS) exchange at very different rates. A correlation exists between the speed of the reaction and the difference between the reduction potential of the incoming cation and that of Zn2+; the larger the difference, the faster the exchange. At the same time, the porosity of the aerogels and the surfactant-free surfaces hold great importance for the exchange reactions, allowing for exchange between cations of similar size and charge (i.e. Pb2+ for Zn2+), a phenomenon that was previously reported as impossible in ligand-capped metal chalcogenide nanoparticles. These observations allowed for a better understanding of the factors governing the cation exchange reaction in nanoscale metal chalcogenides. Quaternary ZnS-CuInS2 gels were obtained by cation exchange with Cu+ and In3+, but the pure CuInS2 phase was not obtained under the mild reaction conditions used, probably due to the very different mobility of the two exchanging cations. The kinetically fast cation exchange process and the propensity of the soft chalcogenide gel networks to bind heavy metal ions selectively, suggest that these materials could also be suitable for the removal of heavy metal ions from the environment. The dissertation research studied the capacity of ZnS aerogels to sequester heavy metal ions such as Pb2+ and Hg2+ from water. The materials are efficient in removing the heavy metal ions from aqueous solutions with a wide range of initial concentrations. For initial concentrations that mimic an environmental spill (i.e. 100 ppb Pb2+), the treatment with the aerogel affords a final concentration lower than the 15 ppm action level recommended by the EPA. Under thermodynamically forcing conditions, the water remediation capacity of the ZnS nanoparticle aerogels was determined to be 14.2 mmol Pb2+ / g ZnS aerogel, which is the highest value reported to date.

Ammonia IRMS-TPD study on the distribution of acid sites in mordenite.

PubMed

Niwa, Miki; Suzuki, Katsuki; Katada, Naonobu; Kanougi, Tomonori; Atoguchi, Takashi

2005-10-13

Using an IRMS-TPD (temperature programmed desorption) of ammonia, we studied the nature, strength, crystallographic location, and distribution of acid sites of mordenite. In this method, infrared spectroscopy (IR) and mass spectroscopy (MS) work together to follow the thermal behavior of adsorbed and desorbed ammonia, respectively; therefore, adsorbed species were identified, and their thermal behavior was directly connected with the desorption of ammonia during an elevation of temperature. IR-measured TPD of the NH4(+) cation was similar to MS-measured TPD, thus showing the nature of Brønsted acidity. From the behavior of OH bands, it was found that the Brønsted acid sites consisted of two kinds of OH bands at high and low wavenumbers, ascribable to OH bands situated on 12- and 8-member rings (MR) of mordenite structure, respectively. The amount and strength of these Brønsted hydroxyls were measured quantitatively based on a theoretical equation using a curve fitting method. Up to ca. 30% of the exchange degree, NH4(+) was exchanged with Na+ on the 12-MR to arrive at saturation; therefore, in this region, the Brønsted acid site was situated on the large pore of 12-MR. The NH4(+) cation was then exchanged with Na+ on 8-MR, and finally exceeded the amount on 12-MR. In the 99% NH4-mordenite, Brønsted acid sites were located predominantly on the 8-MR more than on the 12-MR. Irrespective of the NH4(+) exchange degree, the strengths deltaH of Brønsted OH were 145 and 153 kJ mol(-1) on the 12- and 8-MR, respectively; that is, the strength of Brønsted acid site on the 8-MR was larger than that on the 12-MR. A density functional theory (DFT) calculation supported the difference in the strengths of the acid sites. Catalytic cracking activity of the Brønsted acid sites on the 8-MR declined rapidly, while that on the 12-MR was remarkably kept. The difference in strength and/or steric capacity may cause such a difference in the life of a catalyst.

Polygalacturonase from Rhizopus stolonifer, an Elicitor of Casbene Synthetase Activity in Castor Bean (Ricinus communis L.) Seedlings 1

PubMed Central

Lee, Sung-Chul; West, Charles A.

1981-01-01

Apparently homogeneous polygalacturonase-elicitor purified from the filtrates of Rhizopus stolonifer cultures stimulates germinating castor bean seedlings to produce greatly increased levels of casbene synthetase activity. The purification procedure involved gel-filtration chromatography on Sephadex G-25 and G-75 columns followed by cation-exchange chromatography on a Sephadex CM C-50 column. Homogeneity of the purified preparation was indicated by the results of cationic polyacrylamide disc gel electrophoresis and isoelectric focusing (pI = 8.0). The identity of the casbene elicitor activity and polygalacturonase were indicated by the coincidence of the two activities at all stages of purification, the coincidence of both activities with the single protein-staining band detected on a cationic polyacrylamide disc gel and an isoelectric focusing gel, and the identical behavior of both activities on an agarose gel affinity column. The purified polygalacturonase-elicitor is a glycoprotein with approximately 20% carbohydrate content and an estimated molecular weight of 32,000 by polyacrylamide disc gel electrophoresis. PMID:16661728

Atomic sites and stability of Cs+ captured within zeolitic nanocavities

PubMed Central

Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

2013-01-01

Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations. PMID:23949184

Manufactured soils for plant growth at a lunar base

NASA Technical Reports Server (NTRS)

Ming, Douglas W.

1989-01-01

Advantages and disadvantages of synthetic soils are discussed. It is pointed out that synthetic soils may provide the proper physical and chemical properties necessary to maximize plant growth, such as a toxic-free composition and cation exchange capacities. The importance of nutrient retention, aeration, moisture retention, and mechanical support as qualities for synthetic soils are stressed. Zeoponics, or the cultivation of plants in zeolite substrates that both contain essential plant-growth cations on their exchange sites and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth ions, is discussed. It is suggested that synthetic zeolites at lunar bases could provide adsorption media for separation of various gases, act as catalysts and as molecular sieves, and serve as cation exchangers in sewage-effluent treatment, radioactive-waste disposal, and pollution control. A flow chart of a potential zeoponics system illustrates this process.

Periodic variation in physical and chemical properties of two central Washington soils.

Treesearch

Tom D. Anderson; Arthur R. Tiedemann

1970-01-01

Soils derived from two widely distributed parent materials in central Washington were examined periodically during 1968-69 for physical and chemical properties. Basalt soils showed significant periodic variation in cation exchange capacity, pH, and Na and K contents. In sandstone soils, cation exchange capacity and Ca, Na, and K contents varied significantly among...

Anion exchange of the cationic layered material [Pb2F2]2+.

PubMed

Fei, Honghan; Pham, Catherine H; Oliver, Scott R J

2012-07-04

We demonstrate the complete exchange of the interlamellar anions of a 2-D cationic inorganic material. The α,ω-alkanedisulfonates were exchanged for α,ω-alkanedicarboxylates, leading to two new cationic materials with the same [Pb(2)F(2)](2+) layered architecture. Both were solved by single crystal X-ray diffraction and the transformation also followed by in situ optical microscopy and ex situ powder X-ray diffraction. This report represents a rare example of metal-organic framework displaying highly efficient and complete replacement of its anionic organic linker while retaining the original extended inorganic layer. It also opens up further possibilities for introducing other anions or abatement of problematic anions such as pharmaceuticals and their metabolites.

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.; Pedersen, M.J.

1993-01-01

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Ion exchanger from chemically modified banana leaves.

PubMed

El-Gendy, Ahmed A; Mohamed, Samar H; Abd-Elkader, Amal H

2013-07-25

Cation exchangers from chemically modified banana leaves have been prepared. Banana leaves were treated with different molarities of KMnO4 and cross linked with epichlorohydrin and their effect on metal ion adsorption was investigated. Phosphorylation of chemically modified banana leaves was also studied. The metal ion uptake by these modified banana leaves was clarified. Effect of different varieties, e.g. activation of produced cation exchanger, concentration of metal ions was also investigated. Characterization of the prepared ion exchangers by using infrared and thermal analysis was also taken in consideration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Roles of cation valance and exchange on the retention and colloid-facilitated transport of functionalized multi-walled carbon nanotubes in a natural soil.

PubMed

Zhang, Miaoyue; Bradford, Scott A; Šimůnek, Jirka; Vereecken, Harry; Klumpp, Erwin

2017-02-01

Saturated soil column experiments were conducted to investigate the transport, retention, and release behavior of a low concentration (1 mg L -1 ) of functionalized 14 C-labeled multi-walled carbon nanotubes (MWCNTs) in a natural soil under various solution chemistries. Breakthrough curves (BTCs) for MWCNTS exhibited greater amounts of retardation and retention with increasing solution ionic strength (IS) or in the presence of Ca 2+ in comparison to K + , and retention profiles (RPs) for MWCNTs were hyper-exponential in shape. These BTCs and RPs were well described using the advection-dispersion equation with a term for time- and depth-dependent retention. Fitted values of the retention rate coefficient and the maximum retained concentration of MWCNTs were higher with increasing IS and in the presence of Ca 2+ in comparison to K + . Significant amounts of MWCNT and soil colloid release was observed with a reduction of IS due to expansion of the electrical double layer, especially following cation exchange (when K + displaced Ca 2+ ) that reduced the zeta potential of MWCNTs and the soil. Analysis of MWCNT concentrations in different soil size fractions revealed that >23.6% of the retained MWCNT mass was associated with water-dispersible colloids (WDCs), even though this fraction was only a minor portion of the total soil mass (2.38%). More MWCNTs were retained on the WDC fraction in the presence of Ca 2+ than K + . These findings indicated that some of the released MWCNTs by IS reduction and cation exchange were associated with the released clay fraction, and suggests the potential for facilitated transport of MWCNT by WDCs. Published by Elsevier Ltd.

Sorption and degradation of selected pharmaceuticals in representative soils of the Czech Republic

NASA Astrophysics Data System (ADS)

Kodesova, Radka; Kocarek, Martin; Klement, Ales; Golovko, Oksana; Grabic, Roman; Fer, Miroslav; Nikodem, Antonin; Jaksik, Ondrej

2015-04-01

Knowledge of contaminant behavior (e.g. its sorption onto soil particle, degradation etc.) is essential when assessing contaminant migration in soil and groundwater environment. This study was focused on evaluating sorption isotherms and half-lives for 7 pharmaceuticals (clarithromycin, trimethoprim, metoprolol, atenolol, clindamycin, carbamazepine, sulfamethoxazole) on 13 soils of different soil properties. Sorption of ionizable compounds was highly affected by soil pH. The sorption coefficient of sulfamethoxazole was negatively correlated to soil pH and thus positively related to hydrolytic acidity and exchangeable acidity. Sorption coefficients for clindamycin and clarithromycin were positively related to soil pH and thus negatively related to hydrolytic acidity and exchangeable acidity and positively related to base cation saturation. Sorption coefficients for the remaining pharmaceuticals (trimethoprim, metoprolol, atenolol, and carbamazepine) were also positively correlated with the base cation saturation and cation exchange capacity. Degradation rates in some degree reflected sorption of studied pharmaceuticals on soil particles and increased with decreasing sorption. The highest mobility in studied soils was observed for sulfamethoxazole, but this pharmaceutical was relatively quickly degraded. The second highest mobility was found for carbamazepine, which mostly did not noticeably degrade during our experiments. Thus this pharmaceutical has the highest potential to migrate in water environment. The lowest mobility was observed for clarithromycin. However, this pharmaceutical due to its stability may be retained in an environment for a long time. Acknowledgement: The authors acknowledge the financial support of the Czech Science Foundation (Project No. 13-12477S, Transport of pharmaceuticals in soils). References: Kodesova, R., Grabic, R., Kocarek, M., Klement, A., Golovko, O., Fer, M., Nikodem, A., Jaksik, O., Pharmaceuticals' sorptions relative to properties of thirteen different soils. Science of the Total Environment 511 (2015) 435-443.

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment.

PubMed

Niedbala, Anne; Schaffer, Mario; Licha, Tobias; Nödler, Karsten; Börnick, Hilmar; Ruppert, Hans; Worch, Eckhard

2013-02-01

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 μg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface. Copyright © 2012 Elsevier Ltd. All rights reserved.

Chemical Denudation and Cation Depletion in a Semi-Arid Catchment of the Long-Term Agroecological Research Observatory

NASA Astrophysics Data System (ADS)

Shaljian, M.; Keller, C. K.; Jones, K. B.; Brooks, E. S.; Huggins, D. R.

2016-12-01

The Long-Term Agroecosystem Research (LTAR) network of the USDA is a nationwide observatory and decadal-timescale field-experimental study of sustainable food production. The LTAR thus supports investigation of hydroecological and biogeochemical processes that could affect agricultural sustainability over the course of the 21st century. Mineral-derived nutrient cations are essential to fertility, and acidification of soils due to chemical fertilization may result in unsustainable chemical denudation of the soil exchange pool. Mineral weathering also contributes to base cation denudation. This study investigated base cation losses for one year in drainage from a semi-arid, rain-fed catchment at the Cook Agronomy Farm (CAF) LTAR site in southeastern Washington. We measured flows, analyzed drainage samples and estimated hydrologic effluxes of base cations from the catchment. The total dissolved base cation denudation rate at CAF-LTAR is about 40 kg ha-1 yr-1, which is comparable to other catchments on silicate terranes. The 2.1keq ha-1 yr-1 of denuded cationic charge is dominated by Ca2+ (61%) and Mg2+ (35%). Principal counter-ions are HCO3- (43%), NO3- (38%) and SO42- (16%), suggesting that both H2CO3 and HNO3 are important acids. Comparing 2008 soil pH and base saturation at CAF-LTAR to a nearby native prairie site, we preliminarily estimate a loss of 120 keq ha-1 of base cations from the upper 1.5m of the soil exchangeable cation pool. Dividing this depletion by the estimated denudation flux returns 60 years, which is approximately the interval of chemically intensive agriculture here. This may suggest that the source of exported base cations in drainage is primarily cation exchange rather than mineral weathering. The LTAR observatory will support ongoing monitoring and experimentation necessary to better understand base cation depletion and how it interacts with agroecological changes over the next several decades.

High-pressure alchemy on a small-pore zeolite

NASA Astrophysics Data System (ADS)

Lee, Y.

2011-12-01

While an ever-expanding variety of zeolites with a wide range of framework topology is available, it is desirable to have a way to tailor the chemistry of the zeolitic nanopores for a given framework topology via controlling both the coordination-inclusion chemistry and framework distortion/relaxation. This is, however, subjected to the ability of a zeolitic nanopore to allow the redistribution of cations-water assembly and/or insertion of foreign molecules into the pores and channels. Small-pore zeolites such as natrolite (Na16Al16Si24O80x16H2O), however, have been known to show very limited capacity for any changes in the confinement chemistry. We have recently shown that various cation-exchanged natrolites can be prepared under modest conditions from natural sodium natrolite and exhibit cation-dependent volume expansions by up to 18.5% via converting the elliptical channels into progressively circular ones. Here, we show that pressure can be used as a unique and clean tool to further manipulate the chemistry of the natrolite nanopores. Our recent crystallographic and spectroscopic studies of pressure-insertion of foreign molecules, trivalent-cation exchange under pressure, and pressure-induced inversion of cation-water coordination and pore geometry in various cation-exchanged natrolites will be presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich

Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less

A rice tonoplastic calcium exchanger, OsCCX2 mediates Ca2+/cation transport in yeast

PubMed Central

Yadav, Akhilesh K.; Shankar, Alka; Jha, Saroj K.; Kanwar, Poonam; Pandey, Amita; Pandey, Girdhar K.

2015-01-01

In plant cell, cations gradient in cellular compartments is maintained by synergistic action of various exchangers, pumps and channels. The Arabidopsis exchanger family members (AtCCX3 and AtCCX5) were previously studied and belong to CaCA (calcium cation exchangers) superfamily while none of the rice CCXs has been functionally characterized for their cation transport activities till date. Rice genome encode four CCXs and only OsCCX2 transcript showed differential expression under abiotic stresses and Ca2+ starvation conditions. The OsCCX2 localized to tonoplast and suppresses the Ca2+ sensitivity of K667 (low affinity Ca2+ uptake deficient) yeast mutant under excess CaCl2 conditions. In contrast to AtCCXs, OsCCX2 expressing K667 yeast cells show tolerance towards excess Na+, Li+, Fe2+, Zn2+ and Co2+ and suggest its ability to transport both mono as well as divalent cations in yeast. Additionally, in contrast to previously characterized AtCCXs, OsCCX2 is unable to complement yeast trk1trk2 double mutant suggesting inability to transport K+ in yeast system. These finding suggest that OsCCX2 having distinct metal transport properties than previously characterized plant CCXs. OsCCX2 can be used as potential candidate for enhancing the abiotic stress tolerance in plants as well as for phytoremediation of heavy metal polluted soil. PMID:26607171

Phylogenetic analysis and protein structure modelling identifies distinct Ca(2+)/Cation antiporters and conservation of gene family structure within Arabidopsis and rice species.

PubMed

Pittman, Jon K; Hirschi, Kendal D

2016-12-01

The Ca(2+)/Cation Antiporter (CaCA) superfamily is an ancient and widespread family of ion-coupled cation transporters found in nearly all kingdoms of life. In animals, K(+)-dependent and K(+)-indendent Na(+)/Ca(2+) exchangers (NCKX and NCX) are important CaCA members. Recently it was proposed that all rice and Arabidopsis CaCA proteins should be classified as NCX proteins. Here we performed phylogenetic analysis of CaCA genes and protein structure homology modelling to further characterise members of this transporter superfamily. Phylogenetic analysis of rice and Arabidopsis CaCAs in comparison with selected CaCA members from non-plant species demonstrated that these genes form clearly distinct families, with the H(+)/Cation exchanger (CAX) and cation/Ca(2+) exchanger (CCX) families dominant in higher plants but the NCKX and NCX families absent. NCX-related Mg(2+)/H(+) exchanger (MHX) and CAX-related Na(+)/Ca(2+) exchanger-like (NCL) proteins are instead present. Analysis of genomes of ten closely-related rice species and four Arabidopsis-related species found that CaCA gene family structures are highly conserved within related plants, apart from minor variation. Protein structures were modelled for OsCAX1a and OsMHX1. Despite exhibiting broad structural conservation, there are clear structural differences observed between the different CaCA types. Members of the CaCA superfamily form clearly distinct families with different phylogenetic, structural and functional characteristics, and therefore should not be simply classified as NCX proteins, which should remain as a separate gene family.

NOVEL CONTINUOUS PH/SALT GRADIENT AND PEPTIDE SCORE FOR STRONG CATION EXCHANGE CHROMATOGRAPHY IN 2D-NANO-LC/MSMS PEPTIDE IDENTIFICATION FOR PROTEOMICS

EPA Science Inventory

Tryptic digests of human serum albumin (HSA) and human lung epithelial cell lysates were used as test samples in a novel proteomics study. Peptides were separated and analyzed using 2D-nano-LC/MSMS with strong cation exchange (SCX) and reverse phase (RP) chromatography and contin...

Combination of Cation Exchange and Quantized Ostwald Ripening for Controlling Size Distribution of Lead Chalcogenide Quantum Dots

DOE PAGES

Zhang, Changwang; Xia, Yong; Zhang, Zhiming; ...

2017-03-22

A new strategy for narrowing the size distribution of colloidal quantum dots (QDs) was developed by combining cation exchange and quantized Ostwald ripening. Medium-sized reactant CdS(e) QDs were subjected to cation exchange to form the target PbS(e) QDs, and then small reactant CdS(e) QDs were added which were converted to small PbS(e) dots via cation exchange. The small-sized ensemble of PbS(e) QDs dissolved completely rapidly and released a large amount of monomers, promoting the growth and size-focusing of the medium-sized ensemble of PbS(e) QDs. The addition of small reactant QDs can be repeated to continuously reduce the size distribution. Themore » new method was applied to synthesize PbSe and PbS QDs with extremely narrow size distributions and as a bonus they have hybrid surface passivation. In conclusion, the size distribution of prepared PbSe and PbS QDs are as low as 3.6% and 4.3%, respectively, leading to hexagonal close packing in monolayer and highly ordered three-dimensional superlattice.« less

Combination of Cation Exchange and Quantized Ostwald Ripening for Controlling Size Distribution of Lead Chalcogenide Quantum Dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Changwang; Xia, Yong; Zhang, Zhiming

A new strategy for narrowing the size distribution of colloidal quantum dots (QDs) was developed by combining cation exchange and quantized Ostwald ripening. Medium-sized reactant CdS(e) QDs were subjected to cation exchange to form the target PbS(e) QDs, and then small reactant CdS(e) QDs were added which were converted to small PbS(e) dots via cation exchange. The small-sized ensemble of PbS(e) QDs dissolved completely rapidly and released a large amount of monomers, promoting the growth and size-focusing of the medium-sized ensemble of PbS(e) QDs. The addition of small reactant QDs can be repeated to continuously reduce the size distribution. Themore » new method was applied to synthesize PbSe and PbS QDs with extremely narrow size distributions and as a bonus they have hybrid surface passivation. In conclusion, the size distribution of prepared PbSe and PbS QDs are as low as 3.6% and 4.3%, respectively, leading to hexagonal close packing in monolayer and highly ordered three-dimensional superlattice.« less

High Temperature Thermosetting Polyimide Nanocomposites Prepared with Reduced Charge Organoclay

NASA Technical Reports Server (NTRS)

Campbell, Sandi; Liang, Margaret I.

2005-01-01

The naturally occurring sodium and calcium cations found in bentonite clay galleries were exchanged with lithium cations. Following the cation exchange, a series of reduced charge clays were prepared by heat treatment of the lithium bentonite at 130 C, 150 C, or 170 C. Inductively coupled plasma (ICP) analysis showed that heating the lithium clay at elevated temperatures reduced its cation exchange capacity. Ion exchange of heat-treated clays with either a protonated alkyl amine or a protonated aromatic diamine resulted in decreasing amounts of the organic modifier incorporated into the lithium clay. The level of silicate dispersion in a thermosetting polyimide matrix was dependent upon the temperature of Li-clay heat treatment as well as the organic modification. In general, clays treated at 150 C or 170 C, and exchanged with protonated octadcylamine or protonated 2,2'-dimethlybenzidine (DMBZ) showed a higher degree of dispersion than clays treated at 130 C, or exchanged with protonated dodecylamine. Dynamic mechanical analysis showed little change in the storage modulus or T(sub g) of the nanocomposites compared to the base resin. However, long term isothermal aging of the samples showed a significant decrease in the resin oxidative weight loss. Nanocomposite samples aged in air for 1000 hours at 288 C showed of to a decrease in weight loss compared to that of the base resin. This again was dependent on the temperature at which the Li-clay was heated and the choice of organic modification.

Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

DOEpatents

Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

1998-04-28

A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

Automated protein hydrolysis delivering sample to a solid acid catalyst for amino acid analysis.

PubMed

Masuda, Akiko; Dohmae, Naoshi

2010-11-01

In this study, we developed an automatic protein hydrolysis system using strong cation-exchange resins as solid acid catalysts. Examining several kinds of inorganic solid acids and cation-exchange resins, we found that a few cation-exchange resins worked as acid catalysts for protein hydrolysis when heated in the presence of water. The most efficient resin yielded amounts of amino acids that were over 70% of those recovered after conventional hydrolysis with hydrochloric acid and resulted in amino acid compositions matching the theoretical values. The solid-acid hydrolysis was automated by packing the resin into columns, combining the columns with a high-performance liquid chromatography system, and heating them. The amino acids that constitute a protein can thereby be determined, minimizing contamination from the environment.

Geomaterials: their application to environmental remediation

PubMed Central

Yamada, Hirohisa; Tamura, Kenji; Watanabe, Yujiro; Iyi, Nobuo; Morimoto, Kazuya

2011-01-01

Geomaterials are materials inspired by geological systems originating from the billion years long history of the Earth. This article reviews three important classes of geomaterials. The first one is smectites—layered silicates with a cation-exchange capacity. Smectites are useful for removing pollutants and as intercalation compounds, catalysts and polymer nanocomposites. The second class is layered double hydroxides (LDHs). They have an anion-exchange capacity and are used as catalysts, catalyst precursors, sorbents and scavengers for halogens. The third class of geomaterials is zeolites—microporous materials with a cation-exchange capacity which are used for removing harmful cations. Zeolite composites with LDHs can absorb ammonium and phosphate ions in rivers and lakes, whereas zeolite/apatite composites can immobilize the radioactive iodine. These geomaterials are essential for environmental remediation. PMID:27877455

New Metal Niobate and Silicotitanate Ion Exchangers: Development and Characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexandra Navrotsky; Mary Lou Balmer; Tina M. Nenoff

2003-12-05

This renewal proposal outlines our current progress and future research plans for ion exchangers: novel metal niobate and silicotitanate ion exchangers and their ultimate deployment in the DOE complex. In our original study several forms (including Cs exchanged) of the heat treated Crystalline Silicotitanates (CSTs) were fully characterized by a combination of high temperature synthesis and phase identification, low temperature synthesis and phase identification, and thermodynamics. This renewal proposal is predicated on work completed in our current EMSP program: we have shown preliminary data of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionallymore » high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), in addition to novel silicotitanate phases which are also selective for divalent cations. Furthermore, these materials are easily converted by a high temperature in-situ heat treatment into a refractory ceramic waste form with low cation leachability. The new waste form is a perovskite phase, which is also a major component of Synroc, a titanate ceramic waste form used for sequestration of HLW wastes from reprocessed, spent nuclear fuel. These new niobate ion exchangers also shown orders of magnitude better selectivity for Sr2+ under acid conditions than any other material. The goal of the program is to reduce the costs associated with divalent cation waste removal and disposal, to minimize the risk of contamination to the environment during ion exchanger processing, and to provide DOE with materials for near-term lab-bench stimulant testing, and eventual deployment. The proposed work will provide information on the structure/property relationship between ion exchanger frameworks and selectivity for specific ions, allowing for the eventual ''tuning'' of framework for specific ion exchange needs. To date, DOE sites have become interested in on-site testing of these materials; ongoing discussions and initial experiments are occurring with Dr. Dean Peterman, Idaho National Engineering and Environmental Laboratory (INEEL) (location of the DOE/EM Waste Treatment Focus Area), and Dr. John Harbour, Savannah River Site (SRS). Yet the materials have not been optimized, and further research and development of the novel ion exchangers and testing conditions with simulants are needed. In addition, studies of the ion exchanger composition versus ion selectivity, ion exchange capacity and durability of final waste form are needed. This program will bring together three key institutions to address scientific hurdles of the separation process associated with metal niobate and silicotitanate ion exchangers, in particular for divalent cations (e.g., Sr2+). The program involves a joint effort between researchers at Pacific Northwest National Laboratory, who are leaders in structure/property relations in silicotitanates and in waste form development and performance assessment, Sandia National Laboratories, who discovered and developed crystalline silicotitanate ion exchangers (with Texas A&M and UOP) and also the novel class of divalent metal niobate ion exchangers, and the Thermochemistry Facility at UC Davis, who are world renowned experts in calorimetry and have already performed extensive thermodynamic studies on silicotitanate materials. In addition, Dr. Rodney Ewing of University of Michigan, an expert in radiation effects on materials, and Dr. Robert Roth of the National Institute of Standards and Technology and The Viper Group, a leader in phase equilibria development, will be consultants for radiation and phase studies. The research team will focus on three tasks that will provide both the basic research necessary for the development of highly selective ion exchange materials and also materials for short-term deployment within the DOE complex: (1) Structure/property relationships of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionally high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), (2) the role of ion exchanger structure change (both niobates and silicotitanates) on the exchange capacity (for elements such as Sr and actinide-surrogates) which results from exposure to DOE complex waste simulants, (3) thermodynamic stability of metal niobates and silicotitanate ion exchangers.« less

Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: behavior and XPS study.

PubMed

Pan, Bingjun; Qiu, Hui; Pan, Bingcai; Nie, Guangze; Xiao, Lili; Lv, Lu; Zhang, Weiming; Zhang, Quanxing; Zheng, Shourong

2010-02-01

The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO(3)Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH approximately 4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss. (c) 2009 Elsevier Ltd. All rights reserved.

Chemistry of sustainability-Part I: Carbon dioxide as an organic synthon and Part II: Study of thermodynamics of cation exchange reactions in semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Sathe, Ajay A.

Sustainability is an important part of the design and development of new chemical and energy conversion processes. Simply put sustainability is the ability to meet our needs without sacrificing the ability of the next generations to meet theirs. This thesis describes our efforts in developing two orthogonal strategies for the fixation of CO2 by utilizing high energy intermediates which are generated via oxidative or reductive processes on common organic substrates and of thermochemical measurements of cation exchange reactions which will aid the development of new materials relevant for energy conversion and storage. The first chapter lays a background for the challenges and opportunities for the use of CO2 in organic synthesis. The rapidly growing field of continuous flow processing in organic synthesis is introduced, and its importance in the development of sustainable chemical conversions is highlighted. The second chapter describes the development of a novel route to alpha-amino acids via reductive carboxylation of imines. A mechanistic proposal is presented and the reaction is shown to proceed through the intermediacy of alpha-amino alkyl metal species. Possible strategies for designing catalytic and enantioselective variants of the reaction are presented. The third chapter describes the development of a catalytic oxidative carboxylation of olefins to yield cyclic carbonates. The importance of flow chemistry and membrane separation is demonstrated by allowing the combination of mutually incompatible reagents in a single reaction sequence. While the use of carbon dioxide for synthesis of organic fine chemicals is not expected to help reduce the atmospheric carbon dioxide levels, or tackle climate change, it certainly has the potential to reduce our dependence on non-sustainable carbon feedstocks, and help achieve a carbon neutral chemical life cycle. Having described the use of carbon dioxide and flow chemistry for sustainable chemical conversion, the fourth chapter introduces the role of nanomaterials in sustainable solar energy conversion and storage. The use of cation exchange reactions in nanocrystals to access novel materials is highlighted. Despite having shown tremendous promise in the synthetic applications, the fundamental measurements of the thermodynamic and kinetic parameters of a cation exchange reaction are largely non-existent. This impedes the future growth of this powerful methodology. The technique of isothermal titration calorimetry is introduced, and its importance to studying the thermochemical changes occurring during cation exchange is outlined. The final chapter presents results obtained from the isothermal titration calorimetry on the prototypical cation exchange reaction between cadmium selenide and silver ions. The role of nanoparticle size, identity of the silver salt, solvent, surface ligands and temperature is studied. Recommendations for future investigations using ITC as well as other characterization techniques for discerning the kinetics of cation exchange are presented. I believe that a more unified mechanistic understanding of the cation exchange process in nanomaterials will aid the development of more efficient and robust materials for applications in a wide variety of fields.

Quality characterization of groundwater in Koilsagar project area, Mahabubnagar District, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Raju, C. Sudarsana; Goud, P. V. Prakash

1990-09-01

Studies of groundwater chemistry in the Koilsagar project area of Andhra Pradesh indicate that the waters are sodium bicarbonate, sodium chloride, mixed cationic-mixed anionic, mixed cationic Na dominating bicarbonate, and mixed cationic Ca dominating bicarbonate types. Of them, sodium bicarbonate and mixed cationic Mg dominating bicarbonate types of waters are more prevalent. Isocone mapping of specific conductance indicates that the ionic concentration increases from east to west in the area. Graphical treatment of chemical data reveals that, in general, the area has basic water, whereas the left flank canal area is dominated by secondary alkaline water, and Pallamarri and Pedda Rajmur villages have strongly acidic waters. Ion-exchange studies show that cation-anion exchanges exist all over the area except for two places, which have a base exchange hardened type of water. Graphical representation further shows that most of the area has medium salinity-low sodium (C2S1) water useful for irrigation purposes. High salinity-low sodium (C3S1) and high salinity-medium sodium (C3S2) waters are present in some areas, which need adequate drainage to overcome the salinity problem.

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

DOEpatents

Tompkins, E.R.

1959-02-24

The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

DOE PAGES

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; ...

2017-06-09

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Potassium Niobate Nanolamina: A Promising Adsorbent for Entrapment of Radioactive Cations from Water

PubMed Central

Sun, Jin; Yang, Dongjiang; Sun, Cuihua; Liu, Long; Yang, Shuanglei; (Alec) Jia, Yi; Cai, Rongsheng; Yao, Xiangdong

2014-01-01

Processing and managing radioactive waste is a great challenge worldwide as it is extremely difficult and costly; the radioactive species, cations or anions, leaked into the environment are a serious threat to the health of present and future generations. We report layered potassium niobate (K4Nb6O17) nanolamina as adsorbent to remove toxic Sr2+, Ba2+ and Cs+ cations from wastewater. The results show that K4Nb6O17 nanolamina can permanently confine the toxic cations within the interlayer spacing via a considerable deformation of the metastable layered structure during the ion exchange process. At the same time, the nanolaminar adsorbent exhibits prompt adsorption kinetics, high adsorption capacity and selectivity, and superior acid resistance. These merits make it be a promising material as ion exchanger for the removal of radioactive cations from wastewater. PMID:25472721

Potassium niobate nanolamina: a promising adsorbent for entrapment of radioactive cations from water.

PubMed

Sun, Jin; Yang, Dongjiang; Sun, Cuihua; Liu, Long; Yang, Shuanglei; Alec Jia, Yi; Cai, Rongsheng; Yao, Xiangdong

2014-12-04

Processing and managing radioactive waste is a great challenge worldwide as it is extremely difficult and costly; the radioactive species, cations or anions, leaked into the environment are a serious threat to the health of present and future generations. We report layered potassium niobate (K4Nb6O17) nanolamina as adsorbent to remove toxic Sr(2+), Ba(2+) and Cs(+) cations from wastewater. The results show that K4Nb6O17 nanolamina can permanently confine the toxic cations within the interlayer spacing via a considerable deformation of the metastable layered structure during the ion exchange process. At the same time, the nanolaminar adsorbent exhibits prompt adsorption kinetics, high adsorption capacity and selectivity, and superior acid resistance. These merits make it be a promising material as ion exchanger for the removal of radioactive cations from wastewater.

Rapid Two-Step Procedure for Large-Scale Purification of Pediocin-Like Bacteriocins and Other Cationic Antimicrobial Peptides from Complex Culture Medium

PubMed Central

Uteng, Marianne; Hauge, Håvard Hildeng; Brondz, Ilia; Nissen-Meyer, Jon; Fimland, Gunnar

2002-01-01

A rapid and simple two-step procedure suitable for both small- and large-scale purification of pediocin-like bacteriocins and other cationic peptides has been developed. In the first step, the bacterial culture was applied directly on a cation-exchange column (1-ml cation exchanger per 100-ml cell culture). Bacteria and anionic compounds passed through the column, and cationic bacteriocins were subsequently eluted with 1 M NaCl. In the second step, the bacteriocin fraction was applied on a low-pressure, reverse-phase column and the bacteriocins were detected as major optical density peaks upon elution with propanol. More than 80% of the activity that was initially in the culture supernatant was recovered in both purification steps, and the final bacteriocin preparation was more than 90% pure as judged by analytical reverse-phase chromatography and capillary electrophoresis. PMID:11823243

Biochar production method and composition therefrom

DOEpatents

Lee, James W; Buchanan, III, Archibald C; Evans, Barbara R; Kidder, Michelle K

2014-04-29

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Biochar production method and composition therefrom

DOEpatents

Lee, James W.; Buchanan, III, Archibald C.; Evans, Barbara R.; Kidder, Michelle K.

2013-03-19

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Extraction of cesium and strontium from nuclear waste

DOEpatents

Davis, Jr., Milton W.; Bowers, Jr., Charles B.

1988-01-01

Cesium is extracted from acidified nuclear waste by contacting the waste with a bis 4,4'(5) [1-hydroxy-2-ethylhexyl]benzo 18-crown-6 compound and a cation exchanger in a matrix solution. Strontium is extracted from acidified nuclear waste by contacting the waste with a bis 4,4'(5') [1-hydroxyheptyl]cyclohexo 18-crown-6 compound, and a cation exchanger in a matrix solution.

Catalysis using hydrous metal oxide ion exchanges

DOEpatents

Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

1985-01-01

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Catalysis using hydrous metal oxide ion exchangers

DOEpatents

Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

1983-07-21

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Structural Studies of NH4-exchanged Natrolites at Ambient Conditions and High Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Y Lee; D Seoung; Y Jang

2011-12-31

We report here for the first time that fully and partially NH{sub 4}-exchanged natrolites can be prepared in hydrated states using the solution exchange method with potassium-natrolite. The structural models of the as-prepared hydrated phases and their dehydrated forms at elevated temperature were refined in space group Fdd2 using in situ synchrotron X-ray powder diffraction data and Rietveld methods. The unit-cell volumes of the hydrated NH{sub 4}-exchanged natrolites at ambient conditions, (NH{sub 4}){sub 16(2)}Al{sub 16}Si{sub 24}O{sub 80}{center_dot}14.1(9)H{sub 2}O and (NH{sub 4}){sub 5.1(1)}K{sub 10.9(1)}Al{sub 16}Si{sub 24}O{sub 80}{center_dot}15.7(3)H{sub 2}O, are found to be larger than that the original sodium-natrolite by ca. 15.6%more » and 12.8%, respectively. Upon temperature increase, the fully NH{sub 4}-exchanged natrolite undergoes dehydration at ca. 150 C with ca. 16.4% contraction in the unit-cell volume. The dehydrated phase of the fully NH{sub 4}-exchanged natrolite exhibits marginal volume expansion up to 425 C and then becomes amorphized during temperature decrease and exposure to atmospheric condition. In the case of the partially NH{sub 4}-exchanged natrolite, the dehydration starts from ca. 175 C with {approx}15.1% volume contraction and leads to a partial phase separation to show a phase related to the dehydrated K-natrolite. The degree of the phase separation decreases with temperature increase up to 475 C, concomitant to the gradual volume contraction occurring in the partially NH{sub 4}-exchanged natrolite in the dehydrared state. Upon temperature decrease and exposure to atmospheric condition, only the dehydrated K-natrolite is recovered as a crystalline phase from the partially NH{sub 4}-exchanged natrolite. In the hydrated model of the fully NH{sub 4}-exchanged natrolite, the ammonium cations and water molecules are statistically distributed along the elliptical channels, similar to the disordered pattern observed in natrolites exchanged with larger alkali metal cations such as the K-, Rb-, and Cs-forms. The dehydrated model of the fully NH{sub 4}-exchanged natrolite at 400 C is essentially same as the one reported previously from the sample prepared by direct melt exchange method using sodium-natrolite. Both the hydrated and dehydrated structures of the partially NH{sub 4}-exchanged natrolite at RT and at 400 C, respectively, are characterized by having two separate sites for the ammonium and potassium cations. Comparing the structural models of the monovalent cation forms studied so far, we find that the rotation angle of the natrolite chain is inversely proportional to the cation radius both in the hydrated and dehydrated phases. The distribution pattern of the non-framework species along the natrolite channel also seems to be related to the non-framework cation radius and hence to the chain rotation angle.« less

Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, F. W.

2003-01-01

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

On the Structure-Property Relationships of Cation-Exchanged ZK-5 Zeolites for CO 2 Adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Trong D.; Hudson, Matthew R.; Brown, Craig M.

2017-02-16

The CO 2 adsorption properties of cation-exchanged Li-, Na-, K-, and Mg-ZK-5 zeolites were correlated to the molecular structures determined by Rietveld refinements of synchrotron powder X-ray diffraction patterns. Li-, K-, and Na-ZK-5 all exhibited high isosteric heats of adsorption (Qst) at low CO 2 coverage, with Na-ZK-5 having the highest Qst (ca. 49 kJ mol -1). Mg2+ was located at the center of the zeolite hexagonal prism with the cation inaccessible to CO 2, leading to a much lower Qst (ca. 30 kJ mol-1) and lower overall uptake capacity. Multiple CO 2 adsorption sites were identified at a givenmore » CO 2 loading amount for all four cation-exchanged ZK-5 adsorbents. Site A at the flat eight-membered ring windows and site B/B* in the γ-cages were the primary adsorption sites in Li - and Na-ZK-5 zeolites. Relatively strong dual-cation adsorption sites contributed significantly to an enhanced electrostatic interaction for CO 2 in all ZK-5 samples. This interaction gives rise to a migration of Li + and Mg 2+ cations from their original locations at the center of the hexagonal prisms toward the α-cages, in which they interact more strongly with the adsorbed CO 2.« less

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

NASA Astrophysics Data System (ADS)

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue; Robinson, Richard D.

2014-10-01

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ˜8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

Reduction of non-enzymatic browning of orange juice and semi-concentrates by removal of reaction substrate.

PubMed

Sharma, Satish K; Juyal, Shashibala; Rao, V K; Yadav, V K; Dixit, A K

2014-07-01

A study was conducted to standardize the technology for the removal of amino acids (one of the browning reaction substrates) from sweet orange cv. Malta Common juice to reduce colour and quality deterioration in single strength juice and during subsequent concentration. Juice of sweet orange (Citrus sinensis) cv. Malta Common fruits was extracted by screw type juice extractor, preserved in 500 ppm SO2 and clarified by using "Pectinase CCM" enzyme (0.2% for 2 h at 50 ± 2 °C). For removal of amino acids juice was passed under gravity through a glass column packed with an acidic cation exchange resin (CER), Dowex-50 W and quantity to be treated in one lot was standardized. The CER treated and untreated juices were concentrated to 15 and 30°Brix in a rotary vacuum evaporator. Results indicate that 121 ml of orange juice when passed through a glass column (5 cm internal diameter) packed with cation exchange resin (Dowex-50 W) upto a height of 8 cm, could remove about 98.4% of the amino acids with minimum losses in other juice constituents. With cation exchange resin treatment, the non-enzymatic browning and colour deterioration of orange juice semi-concentrates was reduced to about 3 folds in comparison to untreated counterparts. The retention of vitamin C and sugars was also better in semi-concentrates prepared from cation exchange resin treated juice. Thus, cation exchange resin treatment of orange juice prior to concentration and storage is highly beneficial in reduction of non-enzymatic browning, colour deterioration and retention of nutritional, sensory quality of product during preparation and storage.

Inelastic neutron scattering and molecular simulation of the dynamics of interlayer water in smectite clay minerals

DOE PAGES

Cygan, Randall T.; Daemen, Luke L.; Ilgen, Anastasia G.; ...

2015-11-16

The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to comparemore » the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm –1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Furthermore, divalent cations (Ba 2+ and Mg 2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs + and Na +), which have relatively small hydration enthalpies.« less

Characterization and evaluation of sorption potential of the iron mine waste after Samarco dam disaster in Doce River basin - Brazil.

PubMed

Almeida, Cristiane Aparecida; Oliveira, André Fernando de; Pacheco, Anderson Almeida; Lopes, Renata Pereira; Neves, Antônio Augusto; Lopes Ribeiro de Queiroz, Maria Eliana

2018-06-14

The Fundão dam collapsed releasing 60 million tons of mining waste into the environment. The mining wastes should be better studied, since some of them are deposited on the alluvial plains soil and at the bottom of the rivers, like sediments, of the region affected. Thus, this work aims to perform the chemical, physical and adsorptive characterization of the samples colleted in region de Paracatu de Baixo. The mining waste has uneven surface, with sizes ranging from 2 to 200 μm, pHPCZ in 6.0. Are composed predominantly by kaolinite, goethite, hematite, gibbsite and quartz. It has been classified as non-hazardous residues. The adsorption studies showed the mining waste have a low Cationic Exchange Capacity. The sorption process was occurs by ion exchange and the kinetics follows the pseudo second order model (R 2  > 0.78). The process is endothermic (ΔH in 29.33 kJ mol -1 ) and spontaneous (ΔG in -24.7 kJ mol -1 at 25 °C). The Langmuir model presented a better fit (R 2  > 0.995) to the experimental data. Therefore, the methylene blue can be used as a cation model to predict the behavior of cationic species on the mining waste, with maximum adsorption capacity of 4.42 mg g -1 at 25 °C. Copyright © 2018. Published by Elsevier Ltd.

User`s guide for UTCHEM-5.32m a three dimensional chemical flood simulator. Final report, September 30, 1992--December 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-07-01

UTCHEM is a three-dimensional chemical flooding simulator. The solution scheme is analogous to IMPES, where pressure is solved for implicitly, but concentrations rather than saturations are then solved for explicitly. Phase saturations and concentrations are then solved in a flash routine. An energy balance equation is solved explicitly for reservoir temperature. The energy balance equation includes heat flow between the reservoir and the over-and under-burden rocks. The major physical phenomena modeled in the simulator are: dispersion; dilution effects; adsorption; interfacial tension; relative permeability; capillary trapping; cation exchange; phase density; compositional phase viscosity; phase behavior (pseudoquaternary); aqueous reactions; partitioning of chemicalmore » species between oil and water; dissolution/precipitation; cation exchange reactions involving more than two cations; in-situ generation of surfactant from acidic crude oil; pH dependent adsorption; polymer properties: shear thinning viscosity; inaccessible pore volume; permeability reduction; adsorption; gel properties: viscosity; permeability reduction; adsorption; tracer properties: partitioning; adsorption; radioactive decay; reaction (ester hydrolization); temperature dependent properties: viscosity; tracer reaction; gel reactions The following options are available with UTCHEM: isothermal or non-isothermal conditions, a constant or variable time-step, constant pressure or constant rate well conditions, horizontal and vertical wells, and a radial or Cartesian geometry. Please refer to the dissertation {open_quotes}Field Scale Simulation of Chemical Flooding{close_quotes} by Naji Saad, August, 1989, for a more detailed discussion of the UTCHEM simulator and its formulation.« less

Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

PubMed Central

Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

2012-01-01

This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

Cation exchange in a temporally fluctuating thin freshwater lens on top of saline groundwater

NASA Astrophysics Data System (ADS)

Eeman, S.; De Louw, P. G. B.; Van der Zee, S. E. A. T. M.

2017-01-01

In coastal-zone fields with a high groundwater level and sufficient rainfall, freshwater lenses are formed on top of saline or brackish groundwater. The fresh and the saline water meet at shallow depth, where a transition zone is found. This study investigates the mixing zone that is characterized by this salinity change, as well as by cation exchange processes, and which is forced by seepage and by rainfall which varies as a function of time. The processes are first investigated for a one-dimensional (1D) stream tube perpendicular to the interface concerning salt and major cation composition changes. The complex sequence of changes is explained with basic cation exchange theory. It is also possible to show that the sequence of changes is maintained when a two-dimensional field is considered where the upward saline seepage flows to drains. This illustrates that for cation exchange, the horizontal component (dominant for flow of water) has a small impact on the chemical changes in the vertical direction. The flow's horizontal orientation, parallel to the interface, leads to changes in concentration that are insignificant compared with those that are found perpendicular to the interface, and are accounted for in the 1D flow tube. Near the drains, differences with the 1D considerations are visible, especially in the longer term, exceeding 100 years. The simulations are compared with field data from the Netherlands which reveal similar patterns.

Encapsulation of Ln(III) Ions/Dyes within a Microporous Anionic MOF by Post-synthetic Ionic Exchange Serving as a Ln(III) Ion Probe and Two-Color Luminescent Sensors.

PubMed

Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Feng, Jing; Song, Shu-Yan; Zhang, Hong-Jie

2015-06-26

A new anionic framework {[Me2NH2]0.125[In0.125(H2L)0.25]⋅xDMF}n (1) with one-dimensional (1D) channels along the c axis of about 13.06×13.06 Å(2), was solvothermally synthesized and well characterized. Post-synthetic cation exchange of 1 with Eu(3+), Tb(3+), Dy(3+), Sm(3+) afforded lanthanide(III)-loaded materials, Ln(3+)@1, with different luminescent behavior, indicating that compound 1 could be used as a potential luminescent probe toward different lanthanide(III) ions. Additionally, compound 1 exhibits selective adsorption ability toward cationic dyes. Moreover, the RhB@1 realized the probing of different organic solvent molecules by tuning the energy transfer efficiency between two different emissions, especially for sensing DMF. This work highlights the practical application of luminescent guest@MOFs as sensors, and it paves the way toward other one/multi-color luminescent host-guest systems by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars.

PubMed

Yang, Gang; Wu, Lin; Xian, Qiming; Shen, Fei; Wu, Jun; Zhang, Yanzong

2016-01-01

Biochars, produced by pyrolyzing vermicompost at 300, 500, and 700°C were characterized and their ability to adsorb the dyes Congo red (CR) and Methylene blue (MB) in an aqueous solution was investigated. The physical and chemical properties of biochars varied significantly based on the pyrolysis temperatures. Analysis of the data revealed that the aromaticity, polarity, specific surface area, pH, and ash content of the biochars increased gradually with the increase in pyrolysis temperature, while the cation exchange capacity, and carbon, hydrogen, nitrogen and oxygen contents decreased. The adsorption kinetics of CR and MB were described by pseudo-second-order kinetic models. Both of Langmuir and Temkin model could be employed to describe the adsorption behaviors of CR and MB by these biochars. The biochars generated at higher pyrolysis temperature displayed higher CR adsorption capacities and lower MB adsorption capacities than those compared with the biochars generated at lower pyrolysis temperatures. The biochar generated at the higher pyrolytic temperature displayed the higher ability to adsorb CR owing to its promoted aromaticity, and the cation exchange is the key factor that positively affects adsorption of MB.

Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars

PubMed Central

Yang, Gang; Wu, Lin; Xian, Qiming; Shen, Fei; Wu, Jun; Zhang, Yanzong

2016-01-01

Biochars, produced by pyrolyzing vermicompost at 300, 500, and 700°C were characterized and their ability to adsorb the dyes Congo red (CR) and Methylene blue (MB) in an aqueous solution was investigated. The physical and chemical properties of biochars varied significantly based on the pyrolysis temperatures. Analysis of the data revealed that the aromaticity, polarity, specific surface area, pH, and ash content of the biochars increased gradually with the increase in pyrolysis temperature, while the cation exchange capacity, and carbon, hydrogen, nitrogen and oxygen contents decreased. The adsorption kinetics of CR and MB were described by pseudo-second-order kinetic models. Both of Langmuir and Temkin model could be employed to describe the adsorption behaviors of CR and MB by these biochars. The biochars generated at higher pyrolysis temperature displayed higher CR adsorption capacities and lower MB adsorption capacities than those compared with the biochars generated at lower pyrolysis temperatures. The biochar generated at the higher pyrolytic temperature displayed the higher ability to adsorb CR owing to its promoted aromaticity, and the cation exchange is the key factor that positively affects adsorption of MB. PMID:27144922

Structural behavior of Tl-exchanged natrolite at high pressure depending on the composition of pressure-transmitting medium

NASA Astrophysics Data System (ADS)

Seryotkin, Yu. V.; Bakakin, V. V.; Likhacheva, A. Yu.; Dementiev, S. N.; Rashchenko, S. V.

2017-10-01

The structural evolution of Tl-exchanged natrolite with idealized formula Tl2[Al2Si3O10]·2H2O, compressed in penetrating (water:ethanol 1:1) and non-penetrating (paraffin) media, was studied up to 4 GPa. The presence of Tl+ with non-bonded electron lone pairs, which can be either stereo-chemically active or passive, determines distinctive features of the high-pressure behavior of the Tl-form. The effective volume of assemblages Tl+(O,H2O) n depends on the E-pairs activity: single-sided coordination correlates with smaller volumes. At ambient conditions, there are two types of Tl positions, only one of them having a nearly single-sided coordination as a characteristic of stereo-activity of the Tl+ E pair. Upon the compression in paraffin, a phase transition occurs: a 5% volume contraction of flexible natrolite framework is accompanied by the conversion of all the Tl+ cations into stereo-chemically active state with a single-sided coordination. This effect requires the reconstruction of all the extra-framework subsystems with the inversion of the cation and H2O positions. The compression in water-containing medium leads to the increase of H2O content up to three molecules pfu through the filling of partly vacant positions. This hinders a single-sided coordination of Tl ions and preserves the configuration of their ion-molecular subsystem. It is likely that the extra-framework subsystem is responsible for the super-structure modulation.

Radioactive ion detector

DOEpatents

Bower, Kenneth E.; Weeks, Donald R.

1997-01-01

Apparatus for detecting the presence, in aqueous media, of substances which emit alpha and/or beta radiation and determining the oxidation state of these radioactive substances, that is, whether they are in cationic or anionic form. In one embodiment, a sensor assembly has two elements, one comprised of an ion-exchange material which binds cations and the other comprised of an ion-exchange material which binds anions. Each ion-exchange element is further comprised of a scintillation plastic and a photocurrent generator. When a radioactive substance to which the sensor is exposed binds to either element and emits alpha or beta particles, photons produced in the scintillation plastic illuminate the photocurrent generator of that element. Sensing apparatus senses generator output and thereby indicates whether cationic species or anionic species or both are present and also provides an indication of species quantity.

Radioactive ion detector

DOEpatents

Bower, K.E.; Weeks, D.R.

1997-08-12

Apparatus for detecting the presence, in aqueous media, of substances which emit alpha and/or beta radiation and determining the oxidation state of these radioactive substances, that is, whether they are in cationic or anionic form. In one embodiment, a sensor assembly has two elements, one comprised of an ion-exchange material which binds cations and the other comprised of an ion-exchange material which binds anions. Each ion-exchange element is further comprised of a scintillation plastic and a photocurrent generator. When a radioactive substance to which the sensor is exposed binds to either element and emits alpha or beta particles, photons produced in the scintillation plastic illuminate the photocurrent generator of that element. Sensing apparatus senses generator output and thereby indicates whether cationic species or anionic species or both are present and also provides an indication of species quantity. 2 figs.

Study of the internal morphology of cation-exchange membranes by means of electroosmotic permeability relaxations.

PubMed

Barragán, V M; Izquierdo-Gil, M A; Godino, M P; Villaluenga, J P G

2009-10-01

The effect of an ac sinusoidal perturbation of known amplitude and frequency superimposed to the usual dc applied electric voltage difference on the electroosmotic flow through three cation-exchange membranes with different morphology has been studied. A dispersion of the electroosmotic permeability on the frequency of the applied ac signal has been found for the three membranes investigated, observing that the electroosmotic permeability reaches maximum values for some characteristic values of the frequency. These characteristic frequency values, which are related to relaxation processes in heterogeneous media, depend on the membrane system and permit to obtain information about the different structures of the membrane system. Thus, the study of the electroosmotic permeability relaxation can be used as a method to study the internal morphology of a cation-exchange membrane in a given electrolyte medium.

[Time-evolution study on the cation exchange in the process of reinforcing slip soil by laser-induced breakdown spectroscopy].

PubMed

Liu, Lu-Wen; Zeng, Wei-Li; Zhu, Xiang-Fei; Wu, Jin-Quan; Lin, Zhao-Xiang

2014-03-01

In the present paper, the time evolution study on slip soils treated by different proportions of ionic soil stabilizer (ISS) water solution was conducted by the LIBS system and the relationship between the cation exchange and such engineering properties of reinforcing soil as plasticity index, cohesive force and coefficient of compressibility were analyzed. The results showed that the cation exchange velocity of the proportion of 1:200 ISS reinforcing soil is the fastest among the three proportions (1:100, 1:200 and 1:300) and the modification effect of engineering performance index is quite obvious. These studies provide an experimental basis for the ISS applied to curing project, and monitoring geotechnical engineering performance by LIBS technology also provides a new way of thinking for the curing project monitoring.

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

NASA Astrophysics Data System (ADS)

Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

2016-10-01

Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

Single-stage separation and esterification of cation salt carboxylates using electrodeionization

DOEpatents

Lin, YuPo J.; Henry, Michael; Hestekin, Jamie; Snyder, Seth W.; St. Martin, Edward J.

2006-11-28

A method of and apparatus for continuously making an organic ester from a lower alcohol and an organic acid is disclosed. An organic acid or salt is introduced or produced in an electrode ionization (EDI) stack with a plurality of reaction chambers each formed from a porous solid ion exchange resin wafer interleaved between anion exchange membranes or an anion exchange membrane and a cation exchange membrane or an anion exchange membrane and a bipolar exchange membranes. At least some reaction chambers are esterification chambers and/or bioreactor chambers and/or chambers containing an organic acid or salt. A lower alcohol in the esterification chamber reacts with an anion to form an organic ester and water with at least some of the water splitting with the ions leaving the chamber to drive the reaction.

Time-Resolved Structural Analysis of Cation Exchange Reactions in Birnessite Using Synchrotron XRD

NASA Astrophysics Data System (ADS)

Lopano, C. L.; Heaney, P. J.; Post, J. E.; Hanson, J. C.; Lee, Y.; Komarneni, S.

2002-12-01

Birnessite ((Na,Ca,Mn2+) Mn7O142.8H2O) is a layered Mn-oxide with a 7.2Å spacing between the Mn octahedral sheets. Since birnessite is an abundant phase in soils, desert varnishes, and ocean nodules, it plays a significant role in soil and groundwater chemistry. Experiments by Golden et al. (1986,1987) have demonstrated that Na-buserite (hydrated birnessite) readily exchanges Na+ for a variety of other cations, including K+, Mg2+, Ca2+, Ba2+, Ni2+, and Sr2+. In light of its high cation exchange capacity, birnessite is industrially important for ion and molecular sieves and cathodic materials. In addition, birnessite serves as a precursor in the synthesis of todorokite, which has a 3x3 tunnel structure and is used as an octahedral sieve. We monitored cation-exchange reactions in birnessite by time-resolved X-ray powder diffraction with a simple flow-through cell at the National Synchrotron Light Source. The flow-through cell was developed by Lee and Parise at SUNY-Stony Brook, and this work represents its first application to Mn oxides. A series of synthetic Na-birnessite samples were saturated with chloride solutions containing dissolved K+, Mg2+, and Ba2+, ranging from 0.1M to 0.001M. Powder X-ray diffraction patterns were collected every ~ 3 minutes. The synchrotron experiments revealed that complete cation exchange occurs within three hours, and significant modifications of the arrangements of interlayer cations and water molecules accompany the exchange. Specifically, the replacement of Na by Mg resulted in the continuous growth of a discrete buserite-like phase with a 10Å layer spacing, while replacement of Na by K and Ba retained the 7Å spacing. K replacement of Na resulted in gradually decreasing peak intensity and peak merging. The Ba exchange yielded an abrupt decrease in diffraction intensities followed by a more gradual lattice change over the last 2 hours. Rietveld analysis led to the first determination of the structure of Ba-birnessite in space group C-1. With a final chi-squared parameter of 1.540, the refined lattice parameters were a = 5.178(2)Å, b = 2.850(3)Å, c = 7.320(5)Å, α = 89.512(1)°, β = 102.989(6)°, and γ = 89.893(6)°. However, the lattice parameters of the fully exchanged Ba-birnessite indicate that Ba substitution causes the unit cell to be more monoclinic.

Extraction of cesium and strontium from nuclear waste

DOEpatents

Davis, M.W. Jr.; Bowers, C.B. Jr.

1988-06-07

Cesium is extracted from acidified nuclear waste by contacting the waste with a bis 4,4[prime](5) [1-hydroxy-2-ethylhexyl]benzo 18-crown-6 compound and a cation exchanger in a matrix solution. Strontium is extracted from acidified nuclear waste by contacting the waste with a bis 4,4[prime](5[prime]) [1-hydroxyheptyl]cyclohexo 18-crown-6 compound, and a cation exchanger in a matrix solution. 3 figs.

Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

PubMed

Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

2015-11-16

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

Ga for Zn Cation Exchange Allows for Highly Luminescent and Photostable InZnP-Based Quantum Dots

PubMed Central

2017-01-01

In this work, we demonstrate that a preferential Ga-for-Zn cation exchange is responsible for the increase in photoluminescence that is observed when gallium oleate is added to InZnP alloy QDs. By exposing InZnP QDs with varying Zn/In ratios to gallium oleate and monitoring their optical properties, composition, and size, we conclude that Ga3+ preferentially replaces Zn2+, leading to the formation of InZnP/InGaP core/graded-shell QDs. This cation exchange reaction results in a large increase of the QD photoluminescence, but only for InZnP QDs with Zn/In ≥ 0.5. For InP QDs that do not contain zinc, Ga is most likely incorporated only on the quantum dot surface, and a PL enhancement is not observed. After further growth of a GaP shell and a lattice-matched ZnSeS outer shell, the cation-exchanged InZnP/InGaP QDs continue to exhibit superior PL QY (over 70%) and stability under long-term illumination (840 h, 5 weeks) compared to InZnP cores with the same shells. These results provide important mechanistic insights into recent improvements in InP-based QDs for luminescent applications. PMID:28706347

Multiple-membrane multiple-electrolyte redox flow battery design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Yushan; Gu, Shuang; Gong, Ke

A redox flow battery is provided. The redox flow battery involves multiple-membrane (at least one cation exchange membrane and at least one anion exchange membrane), multiple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and at least one electrolyte disposed between the two membranes) as the basic characteristic, such as a double-membrane, triple electrolyte (DMTE) configuration or a triple-membrane, quadruple electrolyte (TMQE) configuration. The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolytemore » and the positive or negative electrolyte.« less

Erionite-Na upon heating: dehydration dynamics and exchangeable cations mobility

NASA Astrophysics Data System (ADS)

Ballirano, Paolo; Pacella, Alessandro

2016-03-01

Erionite is a fibrous zeolite significantly more tumorigenic than crocidolite asbestos upon inhalation. In recent years, several papers have been published aimed at characterizing from the crystal-chemical point of view erionite fibres. As their toxicity has been ascribed to Fe acquired within the human body, studies aimed at characterizing the iron topochemistry have also been published, suggesting a possible important role played by the ionic exchange properties and cations mobility of this zeolite on developing carcinogenicity. Here we report the analysis results of the thermal behaviour of erionite-Na, which has been found to deviate significantly from that of erionite-K. This result is in contrast with the current scientific view that differences in weighted ionic potential, Si/Al ratio and size of exchangeable cations result in significantly different thermal behaviours, all those parameters being nearly identical or very similar in both species. The different mobility of the extraframework cations observed in erionite samples with dissimilar chemistry is of particular interest within the frame of the hypothesis that their biological activity could depend, apart from surface interactions, also on bulk effects.

Use of a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin column and propionic acid as an eluent in ion-exclusion/adsorption chromatography of aliphatic carboxylic acids and ethanol in food samples.

PubMed

Mori, Masanobu; Hironaga, Takahiro; Kajiwara, Hiroe; Nakatani, Nobutake; Kozaki, Daisuke; Itabashi, Hideyuki; Tanaka, Kazuhiko

2011-01-01

We developed an ion-exclusion/adsorption chromatography (IEAC) method employing a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin (PS-WCX) column with propionic acid as the eluent for the simultaneous determination of multivalent aliphatic carboxylic acids and ethanol in food samples. The PS-WCX column well resolved mono-, di-, and trivalent carboxylic acids in the acidic eluent. Propionic acid as the eluent gave a higher signal-to-noise ratio, and enabled sensitive conductimetric detection of analyte acids. We found the optimal separation condition to be the combination of a PS-WCX column and 20-mM propionic acid. Practical applicability of the developed method was confirmed by using a short precolumn with a strongly acidic cation-exchange resin in the H(+)-form connected before the separation column; this was to remove cations from food samples by converting them to hydrogen ions. Consequently, common carboxylic acids and ethanol in beer, wine, and soy sauce were successfully separated by the developed method.

Fractionation of whey proteins with high-capacity superparamagnetic ion-exchangers.

PubMed

Heebøll-Nielsen, Anders; Justesen, Sune F L; Thomas, Owen R T

2004-09-30

In this study we describe the design, preparation and testing of superparamagnetic anion-exchangers, and their use together with cation-exchangers in the fractionation of bovine whey proteins as a model study for high-gradient magnetic fishing. Adsorbents prepared by attachment of trimethyl amine to particles activated in sequential reactions with allyl bromide and N-bromosuccinimide yielded a maximum bovine serum albumin binding capacity of 156 mg g(-1) combined with a dissociation constant of 0.60 microM, whereas ion-exchangers created by linking polyethylene imine through superficial aldehydes bound up to 337 mg g(-1) with a dissociation constant of 0.042 microM. The latter anion-exchanger was selected for studies of whey protein fractionation. In these, crude bovine whey was treated with a superparamagnetic cation-exchanger to adsorb basic protein species, and the supernatant arising from this treatment was then contacted with the anion-exchanger. For both adsorbent classes of ion-exchanger, desorption selectivity was subsequently studied by sequentially increasing the concentration of NaCl in the elution buffer. In the initial cation-exchange step quantitative removal of lactoferrin (LF) and lactoperoxidase (LPO) was achieved with some simultaneous binding of immunoglobulins (Ig). The immunoglobulins were separated from the other two proteins by desorbing with a low concentration of NaCl (< or = 0.4 M), whereas lactoferrin and lactoperoxidase were co-eluted in significantly purer form, e.g. lactoperoxidase was purified 28-fold over the starting material, when the NaCl concentration was increased to 0.4-1 M. The anion-exchanger adsorbed beta-lactoglobulin (beta-LG) selectively allowing separation from the remaining protein.

Structural and Magnetic Properties of M(mnt)(2) Salts (M = Ni, Pt, Cu) with a Ferrocene-Based Cation, [FcCH(2)N(CH(3))(3)](+). Interplay between M.M and M.S Intermolecular Interactions.

PubMed

Pullen, Anthony E.; Faulmann, Christophe; Pokhodnya, Konstantin I.; Cassoux, Patrick; Tokumoto, Madoka

1998-12-28

A series of metal bis-mnt complexes (mnt = 1,2-dithiolatomaleonitrile) with the trimethylammonium methylferrocene cation have been synthesized and characterized using X-ray diffraction, magnetic susceptibility, and differential scanning calorimetry measurements. The complexes have the formulas (FcCH(2)NMe(3))[Ni(mnt)(2)] (2), (FcCH(2)NMe(3))[Pt(mnt)(2)] (3), and (FcCH(2)NMe(3))(2)[Cu(mnt)(2)] (4) (where Fc = ferrocene). At 300 K, the crystal structures of 1:1 complexes 2 and 3 are very similar. They consist of pairs of [M(mnt)(2)](-) in a slipped configuration packed in stacks. Each [M(mnt)(2)](-) stack is separated from adjacent stacks by two columns of cations. Within the pairs, the [M(mnt)(2)](-) anions interact via short M.S contacts, while there are no short contacts between the pairs. Complex 4, which has a 2:1 stoichiometry, exhibits a markedly different packing arrangement of the anionic units. Due to the special position of the Cu atom in the asymmetric unit cell, [Cu(mnt)(2)](2)(-) dianions are completely isolated from each other. The magnetic susceptibility behavior of the nickel complex is consistent with the presence of magnetically isolated, antiferromagnetically (AF) coupled [Ni(mnt)(2)](-) pairs with the AF exchange parameter, J = -840 cm(-)(1). The platinum complex undergoes an endothermic structural phase transition (T(p)) at 247 K. Below T(p) its structure is characterized by the formation of magnetically isolated [Pt(mnt)(2)](2)(2)(-) dimers in an eclipsed configuration with short Pt.Pt and S.S contacts between monomers. In the magnetic properties, the structural changes reveal themselves as an abrupt susceptibility drop implying a substantial increase of the AF exchange parameter. A mechanism of the phase transition in the platinum compound is proposed. For compound 4, paramagnetic behavior is observed.

Characterization of cross-linked cellulosic ion-exchange adsorbents: 2. Protein sorption and transport.

PubMed

Angelo, James M; Cvetkovic, Aleksandar; Gantier, Rene; Lenhoff, Abraham M

2016-03-18

Adsorption behavior in the HyperCel family of cellulosic ion-exchange materials (Pall Corporation) was characterized using methods to assess, quantitatively and qualitatively, the dynamics of protein uptake as well as static adsorption as a function of ionic strength and protein concentration using several model proteins. The three exchangers studied all presented relatively high adsorptive capacities under low ionic strength conditions, comparable to commercially available resins containing polymer functionalization aimed at increasing that particular characteristic. The strong cation- and anion-exchange moieties showed higher sensitivity to increasing salt concentrations, but protein affinity on the salt-tolerant STAR AX HyperCel exchanger remained strong at ionic strengths normally used in downstream processing to elute material fully during ion-exchange chromatography. Very high uptake rates were observed in both batch kinetics experiments and time-series confocal laser scanning microscopy, suggesting low intraparticle transport resistances relative to external film resistance, even at higher bulk protein concentrations where the opposite is typically observed. Electron microscopy imaging of protein adsorbed phases provided additional insight into particle structure that could not be resolved in previous work on the bare resins. Copyright © 2016 Elsevier B.V. All rights reserved.

A first-principles study of the preventive effects of Al and Mg doping on the degradation in LiNi0.8Co0.1Mn0.1O2 cathode materials.

PubMed

Min, Kyoungmin; Seo, Seung-Woo; Song, You Young; Lee, Hyo Sug; Cho, Eunseog

2017-01-18

First-principles calculations have been used to investigate the effects of Al and Mg doping on the prevention of degradation phenomena in Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 cathode materials. Specifically, we have examined the effects of dopants on the suppression of oxygen evolution and cation disordering, as well as their correlation. It is found that Al doping can suppress the formation of oxygen vacancies effectively, while Mg doping prevents the cation disordering behaviors, i.e., excess Ni and Li/Ni exchange, and Ni migration. This study also demonstrates that formation of oxygen vacancies can facilitate the construction of the cation disordering, and vice versa. Delithiation can increase the probabilities of formation of all defect types, especially oxygen vacancies. When oxygen vacancies are present, Ni can migrate to the Li site during delithiation. However, Al and Mg doping can inhibit Ni migration, even in structures with preformed oxygen defects. The analysis of atomic charge variations during delithiation demonstrates that the degree of oxidation behavior in oxygen atoms is alleviated in the case of Al doping, indicating the enhanced oxygen stability in this structure. In addition, changes in the lattice parameters during delithiation are suppressed in the Mg-doped structure, which suggests that Mg doping may improve the lattice stability.

Effects of exchanged cation on the microporosity of montmorillonite

USGS Publications Warehouse

Rutherford, David W.; Chiou, Cary T.; Eberl, Dennis D.

1997-01-01

The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N2 and neo-hexane by use of t- and αs-plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d(001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo-hexane. In these systems, there was a good consistency of micropore volumes detected by N2 and neo-hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N2 than to relatively large neo-hexane. Hence, the micropore volume as detected by N2 was greater than that detected by neo-hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.

Selective monovalent cation association and exchange around Keplerate polyoxometalate macroanions in dilute aqueous solutions.

PubMed

Pigga, Joseph M; Teprovich, Joseph A; Flowers, Robert A; Antonio, Mark R; Liu, Tianbo

2010-06-15

The interaction between water-soluble Keplerate polyoxometalate {Mo(72)Fe(30)} macroions and small countercations is explored by laser light scattering, anomalous small-angle X-ray scattering (ASAXS), and isothermal titration calorimetry (ITC) techniques. The macroions are found to be able to select the type of associated counterions based upon the counterions' valence state and hydrated size, when multiple types of additional cations are present in solution (even among different monovalent cations). The preference goes to the cations with higher valences or smaller hydrated sizes if the valences are identical. This counterion exchange process changes the magnitude of the macroion-counterion interaction and, thus, is reflected in the dimension of the self-assembled {Mo(72)Fe(30)} blackberry supramolecular structures. The hydrophilic macroions exhibit a competitive recognition of various monovalent counterions in dilute solutions. A critical salt concentration (CSC) for each type of cation exists for the blackberry formation of {Mo(72)Fe(30)} macroions, above which the blackberry size increases significantly with the increasing total ionic strength in solution. The CSC values are much smaller for cations with higher valences and also decrease with the cations' hydrated size for various monovalent cations. The change of blackberry size corresponding to the change of ionic strength in solution is reversible.

Electrochemically Switchable Polymeric Membrane Ion-Selective Electrodes.

PubMed

Zdrachek, Elena; Bakker, Eric

2018-06-07

We present here for the first time a solid contact ion-selective electrode suitable for the simultaneous sensing of cations (tetrabutylammonium) and anions (hexafluorophosphate), achieved by electrochemical switching. The membrane is based on a thin plasticized polyurethane membrane deposited on poly(3-octylthiophene) (POT) and contains a cation exchanger and lipophilic electrolyte (ETH 500). The cation exchanger is initially in excess; the ion-selective electrode exhibits an initial potentiometric response to cations. During an oxidative current pulse, POT is converted into POT + , which results in the expulsion of cations from the membrane followed by the extraction of anions from the sample solution to fulfill the electroneutrality condition. This creates a defined excess of lipophilic cation in the membrane, resulting in a potentiometric anion response. A reductive current pulse restores the original cation response by triggering the conversion of POT + back into POT, which is accompanied by the expulsion of anions from the membrane and the extraction of cations from the sample solution. Various current pulse magnitudes and durations are explored, and the best results in terms of response slope values and signal stability were observed with an oxidation current pulse of 140 μA cm -2 applied for 8 s and a reduction current pulse of -71 μA cm -2 applied for 8 s.

SEPARATING HAFNIUM FROM ZIRCONIUM

DOEpatents

Lister, B.A.J.; Duncan, J.F.

1956-08-21

A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes

PubMed Central

Arges, Christopher G.; Ramani, Vijay

2013-01-01

Anion exchange membranes (AEMs) find widespread applications as an electrolyte and/or electrode binder in fuel cells, electrodialysis stacks, flow and metal-air batteries, and electrolyzers. AEMs exhibit poor stability in alkaline media; their degradation is induced by the hydroxide ion, a potent nucleophile. We have used 2D NMR techniques to investigate polymer backbone stability (as opposed to cation stability) of the AEM in alkaline media. We report the mechanism behind a peculiar, often-observed phenomenon, wherein a demonstrably stable polysulfone backbone degrades rapidly in alkaline solutions upon derivatization with alkaline stable fixed cation groups. Using COSY and heteronuclear multiple quantum correlation spectroscopy (2D NMR), we unequivocally demonstrate that the added cation group triggers degradation of the polymer backbone in alkaline via quaternary carbon hydrolysis and ether hydrolysis, leading to rapid failure. This finding challenges the existing perception that having a stable cation moiety is sufficient to yield a stable AEM and emphasizes the importance of the often ignored issue of backbone stability. PMID:23335629

Enrichment and low-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in drinking water after cleanup by cation exchange resin.

PubMed

Küsters, Markus; Gerhartz, Michael

2010-04-01

For the determination of glyphosate, aminomethylphosphonic acid and glufosinate in drinking water, different procedures of enrichment and cleanup were examined using anion exchange or SPE. In many cases interactions of, e.g. alkaline earth metal ions especially calcium could be observed during enrichment and cleanup resulting in loss of analytes. For that reason, a novel cleanup and enrichment procedure for the determination of these phosphonic acid herbicides has been developed in drinking water using cation-exchange resin. In summary, the cleanup procedure with cation-exchange resin developed in this study avoids interactions as described above and is applicable to calcium-rich drinking water samples. After derivatization with 9-fluorenylmethylchloroformate followed by LC with fluorescence detection, LOD of 12, 14 and 12 ng/L and mean recoveries from real-world drinking water samples of 98+/-9, 100+/-16 and 101+/-11% were obtained for glyphosate, aminomethylphosphonic acid and glufosinate, respectively. The low LODs and the high precision permit the analysis of these phosphonic acid herbicides according to the guidelines of the European Commission.

Anomalous magnetic properties of 7 nm single-crystal Co3O4 nanowires

NASA Astrophysics Data System (ADS)

Lv, Ping; Zhang, Yan; Xu, Rui; Nie, Jia-Cai; He, Lin

2012-01-01

We present a study of magnetic properties of single-crystal Co3O4 nanowires with diameter about 7 nm. The nanowires expose (111) planes composed of plenty of Co3+ cations and exhibit two order temperatures at 56 K (TN of wire cores) and 73 K (order temperature of wire shells), which are far above TN = 40 K of bulk Co3O4. This novel behavior is attributed to symmetry breaking of surface Co3+ cations and magnetic proximity effect. The nanowire shells show macroscopic residual magnetic moments. Cooling in a magnetic field, a fraction of the residual moments are tightly pinned to the antiferromagnetic lattice, which results in an obvious horizontal and vertical shift of hysteresis loop. Our experiment demonstrates that the exchange bias field HE and the pinned magnetic moments Mpin follow a simple expression HE = aMpin with a a constant.

ADSORPTION METHOD FOR SEPARATING METAL CATIONS

DOEpatents

Khym, J.X.

1959-03-10

The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

Activation of a Ca-bentonite as buffer material

NASA Astrophysics Data System (ADS)

Huang, Wei-Hsing; Chen, Wen-Chuan

2016-04-01

Swelling behavior is an important criterion in achieving the low-permeability sealing function of buffer material. A potential buffer material may be used for radioactive waste repository in Taiwan is a locally available clayey material known as Zhisin clay, which has been identified as a Ca-bentonite. Due to its Ca-based origin, Zhisin was found to exhibit swelling capacity much lower than that of Na-bentonite. To enhance the swelling potential of Zhisin clay, a cation exchange process by addition of Na2CO3 powder was introduced in this paper. The addition of Na2CO3 reagent to Zhisin clay, in a liquid phase, caused the precipitation of CaCO3 and thereby induced a replacement of Ca2+ ions by Na+ ions on the surface of bentonite. Characterization test conducted on Zhisin clay includes chemical analysis, cation exchange capacity, X-ray diffraction, and thermogravimetry (TG). Free-swelling test apparatus was developed according to International Society of Rock Mechanics recommendations. A series of free-swelling tests were conducted on untreated and activated specimens to characterize the effect of activation on the swelling capacity of Zhisin clay. Efforts were made to determine an optimum dosage for the activation, and to evaluate the aging effect. Also, the activated material was evaluated for its stability in various hydrothermal conditions for potential applications as buffer material in a repository. Experimental results show that Na2CO3-activated Zhisin clay is superior in swelling potential to untreated Zhisin clay. Also, there exists an optimum amount of activator in terms of improvements in the swelling capacity. A distinct time-swell relationship was discovered for activated Zhisin clay. The corresponding mechanism refers to exchange of cations and breakdown of quasi-crystal, which results in ion exchange hysteresis of Ca-bentonite. Due to the ion exchange hysteresis, activated bentonite shows a post-rise time-swell relationship different than the sigmoid-shaped time-swell curves of typical bentonites. That is, a greater part of swelling strain develops after the completion of primary swelling strain. At an optimal amount of 1% Na2CO3 in weight, the maximum swelling strain was found to be 3 times as much as that of untreated Zhisin clay. Furthermore, the Na2CO3-activated Zhisin clay exhibited improved resistance to thermal environments and behaved similar to Na-type bentonites under various hydrothermal temperatures.

Method of separating and recovering uranium and related cations from spent Purex-type systems

DOEpatents

Mailen, J.C.; Tallent, O.K.

1987-02-25

A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

Retardation of ammonium and potassium transport through a contaminated sand and gravel aquifer: The Role of cation exchange

USGS Publications Warehouse

Ceazan, M.L.; Thurman, E.M.; Smith, R.L.

1989-01-01

The role of cation exchange in the retardation of ammonium (NH4+) and potassium (K+) transport in a shallow sand and gravel aquifer was evaluated by use of observed distributions of NH4+ and K+ within a plume of sewage-contaminated groundwater, small-scale tracer injection tests, and batch sorption experiments on aquifer material. Both NH4+ and K+ were transported ???2 km in the 4-km-long contaminant plume (retardation factor, Rf = 2.0). Sediments from the NH4+-containing zone of the plume contained significant quantities of KCl-extractable NH4+ (extraction distribution coefficient, Kd,extr = 0.59-0.87 mL/g of dry sediment), and when added to uncontaminated sediments, NH4+ sorption followed a linear isotherm. Small-scale tracer tests demonstrated that NH4+ and K+ were retarded (Rf =3.5) relative to a nonreactive tracer (Br-). Sorption of dissolved NH4+ was accompanied by concomitant release of calcium (Ca2+), magnesium (Mg2+), and sodium (Na+) from aquifer sediments, suggesting involvement of cation exchange. In contrast, nitrate (NO3-) was not retarded and cleanly separated from NH4+ and K+ in the small-scale tracer tests. This study demonstrates that transport of NH4+ and K+ through a sand and gravel aquifer can be markedly affected by cation-exchange processes even at a clay content less than 0.1%.

Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

USGS Publications Warehouse

Lerch, R.N.; Thurman, E.M.; Kruger, E.L.

1997-01-01

This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

A weak cation-exchange monolith as stationary phase for the separation of peptide diastereomers by CEC.

PubMed

Ludewig, Ronny; Nietzsche, Sandor; Scriba, Gerhard K E

2011-01-01

A CEC weak cation-exchange monolith has been prepared by in situ polymerization of acrylamide, methylenebisacrylamide and 4-acrylamidobutyric acid in a decanol-dimethylsulfoxide mixture as porogen. The columns were evaluated by SEM and characterized with regard to the separation of diastereomers and α/β-isomers of aspartyl peptides. Column preparation was reproducible as evidenced by comparison of the analyte retention times of several columns prepared simultaneously. Analyte separation was achieved using mobile phases consisting of acidic phosphate buffer and ACN. Under these conditions the peptides migrated due to their electrophoretic mobility but the EOF also contributed as driving force as a function of the pH of the mobile phase due to increasing dissociation of the carboxyl groups of the polymer. Raising the pH of the mobile phase also resulted in deprotonation of the peptides reducing analyte mobility. Due to these mechanisms each pair of diastereomeric peptides displayed the highest resolution at a different pH of the buffer component of the mobile phase. Comparing the weak-cation exchange monolith to an RP monolith and a strong cation-exchange monolith different elution order of some peptide diastereomers was observed, clearly illustrating that interactions with the stationary phase contribute to the CEC separations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tetracycline adsorption on kaolinite: pH, metal cations and humic acid effects.

PubMed

Zhao, Yanping; Geng, Jinju; Wang, Xiaorong; Gu, Xueyuan; Gao, Shixiang

2011-07-01

Contamination of environmental matrixes by human and animal wastes containing antibiotics is a growing health concern. Because tetracycline is one of the most widely-used antibiotics in the world, it is important to understand the factors that influence its mobility in soils. This study investigated the effects of pH, background electrolyte cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), heavy metal Cu(2+) and humic acid (HA) on tetracycline adsorption onto kaolinite. Results showed that tetracycline was greatly adsorbed by kaolinite over pH 3-6, then decreased with the increase of pH, indicating that tetracycline adsorption mainly through ion exchange of cations species and complexation of zwitterions species. In the presence of five types of cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), tetracycline adsorption decreased in accordance with the increasing of atomic radius and valence of metal cations, which suggested that outer-sphere complexes formed between tetracycline and kaolinite, and the existence of competitor ions lead to the decreasing adsorption. The presence of Cu(2+) greatly enhanced the adsorption probably by acting as a bridge ion between tetracycline species and the edge sites of kaolinite. HA also showed a major effect on the adsorption: at pH < 6, the presence of HA increased the adsorption, while the addition of HA showed little effect on tetracycline adsorption at higher pH. The soil environmental conditions, like pH, metal cations and soil organic matter, strongly influence the adsorption behavior of tetracycline onto kaolinite and need to be considered when assessing the environmental toxicity of tetracycline.

Characterization of the cation-binding capacity of a potassium-adsorption filter used in red blood cell transfusion.

PubMed

Suzuki, Takao; Muto, Shigeaki; Miyata, Yukio; Maeda, Takao; Odate, Takayuki; Shimanaka, Kimio; Kusano, Eiji

2015-06-01

A K(+) -adsorption filter was developed to exchange K(+) in the supernatant of stored irradiated red blood cells with Na(+) . To date, however, the filter's adsorption capacity for K(+) has not been fully evaluated. Therefore, we characterized the cation-binding capacity of this filter. Artificial solutions containing various cations were continuously passed through the filter in 30 mL of sodium polystyrene sulfonate at 10 mL/min using an infusion pump at room temperature. The cation concentrations were measured before and during filtration. When a single solution containing K(+) , Li(+) , H(+) , Mg(2+) , Ca(2+) , or Al(3+) was continuously passed through the filter, the filter adsorbed K(+) and the other cations in exchange for Na(+) in direct proportion to the valence number. The order of affinity for cation adsorption to the filter was Ca(2+) >Mg(2+) >K(+) >H(+) >Li(+) . In K(+) -saturated conditions, the filter also adsorbed Na(+) . After complete adsorption of these cations on the filter, their concentration in the effluent increased in a sigmoidal manner over time. Cations that were bound to the filter were released if a second cation was passed through the filter, despite the different affinities of the two cations. The ability of the filter to bind cations, especially K(+) , should be helpful when it is used for red blood cell transfusion at the bedside. The filter may also be useful to gain a better understanding of the pharmacological properties of sodium polystyrene sulfonate. © 2015 The Authors. Therapeutic Apheresis and Dialysis © 2015 International Society for Apheresis.

Yb3O(OH)6Cl·2H2O: an anion-exchangeable hydroxide with a cationic inorganic framework structure.

PubMed

Goulding, Helen V; Hulse, Sarah E; Clegg, William; Harrington, Ross W; Playford, Helen Y; Walton, Richard I; Fogg, Andrew M

2010-10-06

The first anion-exchangeable framework hydroxide, Yb(3)O(OH)(6)Cl·2H(2)O, has been synthesized hydrothermally. This material has a three-dimensional cationic ytterbium oxyhydroxide framework with one-dimensional channels running through the structure in which the chloride anions and water molecules are located. The framework is thermally stable below 200 °C and can be reversibly dehydrated and rehydrated with no loss of crystallinity. Additionally, it is able to undergo anion-exchange reactions with small ions such as carbonate, oxalate, and succinate with retention of the framework structure.

Mixed-bed ion exchange chromatography employing a salt-free pH gradient for improved sensitivity and compatibility in MudPIT.

PubMed

Mommen, Geert P M; Meiring, Hugo D; Heck, Albert J R; de Jong, Ad P J M

2013-07-16

In proteomics, comprehensive analysis of peptides mixtures necessitates multiple dimensions of separation prior to mass spectrometry analysis to reduce sample complexity and increase the dynamic range of analysis. The main goal of this work was to improve the performance of (online) multidimensional protein identification technology (MudPIT) in terms of sensitivity, compatibility and recovery. The method employs weak anion and strong cation mixed-bed ion exchange chromatography (ACE) in the first separation dimension and reversed phase chromatography (RP) in the second separation dimension (Motoyama et.al. Anal. Chem 2007, 79, 3623-34.). We demonstrated that the chromatographic behavior of peptides in ACE chromatography depends on both the WAX/SCX mixing ratio as the ionic strength of the mobile phase system. This property allowed us to replace the conventional salt gradient by a (discontinuous) salt-free, pH gradient. First dimensional separation of peptides was accomplished with mixtures of aqueous formic acid and dimethylsulfoxide with increasing concentrations. The overall performance of this mobile phase system was found comparable to ammonium acetate buffers in application to ACE chromatography, but clearly outperformed strong cation exchange for use in first dimensional peptide separation. The dramatically improved compatibility between (salt-free) ion exchange chromatography and reversed phase chromatography-mass spectrometry allowed us to downscale the dimensions of the RP analytical column down to 25 μm i.d. for an additional 2- to 3-fold improvement in performance compared to current technology. The achieved levels of sensitivity, orthogonality, and compatibility demonstrates the potential of salt-free ACE MudPIT for the ultrasensitive, multidimensional analysis of very modest amounts of sample material.

Systematic generation of buffer systems for pH gradient ion exchange chromatography and their application.

PubMed

Kröner, Frieder; Hubbuch, Jürgen

2013-04-12

pH gradient protein separations are widely used techniques in the field of protein analytics, of which isoelectric focusing is the most well known application. The chromatographic variant, based on the formation of pH gradients in ion exchange columns is only rarely applied due to the difficulties to form controllable, linear pH gradients over a broad pH range. This work describes a method for the systematic generation of buffer compositions with linear titration curves, resulting in well controllable pH gradients. To generate buffer compositions with linear titration curves an in silico method was successfully developed. With this tool, buffer compositions for pH gradient ion exchange chromatography with pH ranges spanning up to 7.5 pH units were established and successfully validated. Subsequently, the buffer systems were used to characterize the elution behavior of 22 different model proteins in cation and anion exchange pH gradient chromatography. The results of both chromatographic modes as well as isoelectric focusing were compared to describe differences in between the methods. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of a High-Throughput Ion-Exchange Resin Characterization Workflow.

PubMed

Liu, Chun; Dermody, Daniel; Harris, Keith; Boomgaard, Thomas; Sweeney, Jeff; Gisch, Daryl; Goltz, Bob

2017-06-12

A novel high-throughout (HTR) ion-exchange (IEX) resin workflow has been developed for characterizing ion exchange equilibrium of commercial and experimental IEX resins against a range of different applications where water environment differs from site to site. Because of its much higher throughput, design of experiment (DOE) methodology can be easily applied for studying the effects of multiple factors on resin performance. Two case studies will be presented to illustrate the efficacy of the combined HTR workflow and DOE method. In case study one, a series of anion exchange resins have been screened for selective removal of NO 3 - and NO 2 - in water environments consisting of multiple other anions, varied pH, and ionic strength. The response surface model (RSM) is developed to statistically correlate the resin performance with the water composition and predict the best resin candidate. In case study two, the same HTR workflow and DOE method have been applied for screening different cation exchange resins in terms of the selective removal of Mg 2+ , Ca 2+ , and Ba 2+ from high total dissolved salt (TDS) water. A master DOE model including all of the cation exchange resins is created to predict divalent cation removal by different IEX resins under specific conditions, from which the best resin candidates can be identified. The successful adoption of HTR workflow and DOE method for studying the ion exchange of IEX resins can significantly reduce the resources and time to address industry and application needs.

Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

NASA Technical Reports Server (NTRS)

Allen, E. R.; Hossner, L. R.; Ming, D. W.; Henninger, D. L.

1993-01-01

Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caldwell, Andrew H.; Ha, Don-Hyung; Robinson, Richard D., E-mail: rdr82@cornell.edu

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less

Impact of monovalent cations on soil structure. Part I. Results of an Iranian soil

NASA Astrophysics Data System (ADS)

Farahani, Elham; Emami, Hojat; Keller, Thomas; Fotovat, Amir; Khorassani, Reza

2018-01-01

This study investigated the impact of monovalent cations on clay dispersion, aggregate stability, soil pore size distribution, and saturated hydraulic conductivity on agricultural soil in Iran. The soil was incubated with treatment solutions containing different concentrations (0-54.4 mmol l-1) of potassium and sodium cations. The treatment solutions included two levels of electrical conductivity (EC=3 or 6 dS m-1) and six K:Na ratios per electrical conductivity level. At both electrical conductivity levels, spontaneously dispersible clay increased with increasing K concentration, and with increasing K:Na ratio. A negative linear relationship between percentage of water-stable aggregates and spontaneously dispersible clay was observed. Clay dispersion generally reduced the mean pore size, presumably due to clogging of pores, resulting in increased water retention. At both electrical conductivity levels, hydraulic conductivity increased with increasing exchangeable potassium percentage at low exchangeable potassium percentage values, but decreased with further increases in exchangeable potassium percentage at higher exchangeable potassium percentage. This is in agreement with earlier studies, but seems in conflict with our data showing increasing spontaneously dispersible clay with increasing exchangeable potassium percentage. Our findings show that clay dispersion increased with increasing K concentration and increasing K:Na ratio, demonstrating that K can have negative impacts on soil structure.

UTILITY OF ZEOLITES IN ARSENIC REMOVAL FROM WATER

EPA Science Inventory

Zeolites are well known for their ion exchange and adsorption properties. So far the cation exchanger properties of zeolites have been extensively studied and utilized. The anion exchanger properties of zeolites are less studied. Zeolite Faujasite Y has been used to remove arseni...

Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

PubMed

Fischer, Michael; Bell, Robert G

2014-10-21

The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount of energy required for regeneration. In this respect, SAPOs exchanged with alkaline earth cations could provide a better balance between selectivity and energy cost of regeneration.

Modeling salinization and recovery of road salt-impacted lakes in temperate regions based on long-term monitoring of Lake George, New York (USA) and its drainage basin.

PubMed

Sutherland, J W; Norton, S A; Short, J W; Navitsky, C

2018-05-08

Road salt mitigates winter highway icing but accumulates in watershed soils and receiving waters, affecting soil chemistry and physical, biological, and ecological processes. Despite efforts to reduce salt loading in watersheds, accumulated cations and Cl - continue to impact tributaries and lakes, and the recovery process is not well understood. Lake George, New York (USA) is typical of many temperate lakes at risk for elevated Cl - concentrations from winter deicing; the lake salt concentration increased by ~3.4% year -1 since 1980. Here, we evaluated the ionic composition in Finkle Brook, a major watershed draining to Lake George, studied intermittently since 1970 and typical of other salt-impacted Lake George tributaries. Salt loading in the Lake George basin since the 1940s displaced cations from exchange sites in basin soils; these desorbed cations follow a simple ion-exchange model, with lower sodium and higher calcium, magnesium and potassium fluxes in runoff. Reduced salt application in the Finkle Brook watershed during the low-snow winter of 2015-2016 led to a 30-40% decline of Cl - and base cations in the tributary, implying a Cl - soil half-life of 1-2 years. We developed a conceptual model that describes cation behavior in runoff from a watershed that received road salt loading over a long period of time, and then recovery following reduced salt loading. Next, we developed a dynamic model estimating time to steady-state for Cl - in Lake George with road salt loading starting in 1940, calibrating the model with tributary runoff and lake chemistry data from 1970 and 1980, respectively, and forecasting Cl - concentrations in Lake George based on various scenarios of salt loading and soil retention of Cl - . Our Lake George models are readily adaptable to other temperate lakes with drainage basins where road salt is applied during freezing conditions and paved roads cover a portion of the watershed. Copyright © 2018 Elsevier B.V. All rights reserved.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato

2001-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato; Gula, Michael J.; Xue, Sui; Harvey, James T.

2002-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Evaluation of Zeolite Permeable Treatment Wall for the Removal of Strontium-90 from Groundwater

NASA Astrophysics Data System (ADS)

Seneca, S. M.; Bandilla, K.; Rabideau, A. J.; Ross, E.; Bronner, C. E.

2009-12-01

Experimental and modeling studies are in progress to evaluate the potential performance of a permeable treatment wall comprised of zeolite-rich rock for the removal of strontium-90 from groundwater. Column studies were performed using a synthetic groundwater referenced to anticipate field conditions, with a focus on quantifying the competitive ion exchange among five cations (Na+, K+, Ca2+, Mg2+, and Sr2+). Ongoing studies are focused on the comparison of zeolites obtained from two sources: Teague Mineral Products (Adrian, OR) and Bear River Zeolite (Preston, UT), and on the possible influence of native soil that is mixed with treatment wall material during construction. The data obtained from the column studies is used to support robust estimation of zeolite cation exchange parameters producing a five-solute cation exchange model describing the removal efficiency of the zeolite. The field-scale transport model provides flexibility to explore design parameters to support the possible deployment of a full scale treatment wall at a Western New York nuclear facility.

Toward Separating Alpha-lactalbumin and Beta-lactoglobulin Proteins from Whey through Cation-exchange Adsorption

NASA Astrophysics Data System (ADS)

El-Sayed, Mayyada; Chase, Howard

2009-05-01

This paper describes the cation-exchange adsorption of the two major whey proteins, alpha-lactalbumin (ALA) and beta-lactoglobulin (BLG) with the purpose of establishing a process for isolating them from cow's milk whey. The single- and two-component adsorption of 1.5 mg/ml ALA and 3 mg/ml BLG to the cation-exchanger SP Sepharose FF at 20° C using 0.1 M acetate buffer of pH 3.7 was studied. Langmuir isotherm parameters were determined for the pure proteins. In two-component systems, BLG breakthrough curve exhibited an overshoot phenomenon that gave evidence for the presence of a competitive adsorption between the two proteins. Complete separation occurred and it was possible to obtain each of the two proteins in a pure form. The process was then applied to a whey concentrate mixture where incomplete separation took place. However, BLG was produced with 95% purity and a recovery of 80%, while ALA showed an 84% recovery with low purity.

pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays

NASA Technical Reports Server (NTRS)

Lawless, J. G.; Church, F. M.; Mazzurco, J.; Banin, A.; Huff, R.; Kao, J.; Cook, A.; Lowe, T.; Orenberg, J. B.; Edelson, E.

1985-01-01

The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.

First Cationic Uranyl-Organic Framework with Anion-Exchange Capabilities.

PubMed

Bai, Zhuanling; Wang, Yanlong; Li, Yuxiang; Liu, Wei; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

2016-07-05

By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl-organic framework [(UO2)2(TTTPC)(OH)O(COOH)]·1.5DMF·7H2O (SCU-6) to the first cationic uranyl-organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br·1.5DMF·4H2O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4(-)-exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 × 10(-5) S cm(-1) at 50 °C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material.

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE PAGES

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; ...

2016-01-22

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

A Cation-containing Polymer Anion Exchange Membrane based on Poly(norbornene)

NASA Astrophysics Data System (ADS)

Beyer, Frederick; Price, Samuel; Ren, Xiaoming; Savage, Alice

Cation-containing polymers are being studied widely for use as anion exchange membranes (AEMs) in alkaline fuel cells (AFCs) because AEMs offer a number of potential benefits including allowing a solid state device and elimination of the carbonate poisoning problem. The successful AEM will combine high performance from several orthogonal properties, having robust mechanical strength even when wet, high hydroxide conductivity, and the high chemical stability required for long device lifetimes. In this study, we have synthesized a model cationic polymer that combines three of the key advantages of Nafion. The polymer backbone based on semicrystalline atactic poly(norbornene) offers good mechanical properties. A flexible, ether-based tether between the backbone and fixed cation charged species (quaternary ammonium) should provide the low-Tg, hydrophilic environment required to facilitate OH- transport. Finally, methyl groups have been added at the beta position relative to the quaternary ammonium cation to prevent Hoffman elimination, one mechanism by which AEMs are neutralized in a high pH environment. In this poster, we will present our findings on mechanical properties, morphology, charge transport, and chemical stability of this material.

Ion-exclusion/cation-exchange chromatography with dual detection of the conductivity and spectrophotometry for the simultaneous determination of common inorganic anionic species and cations in river and wastewater.

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Mori, Masanobu; Hasebe, Kiyoshi; Nakagoshi, Nobukazu; Tanaka, Kazuhiko

2011-01-01

Simultaneous determinations of common inorganic anionic species (SO(4)(2-), Cl(-), NO(3)(-), phosphate and silicate) and cations (Na(+), NH(4)(+), K(+), Mg(2+) and Ca(2+)) were conducted using an ion-chromatography system with dual detection of conductivity and spectrophotometry in tandem. The separation of ionic species on a weakly acidic cation-exchange resin was accomplished using a mixture of 100 mM ascorbic acid and 4 mM 18-crown-6 as an acidic eluent (pH 2.6), after which the ions were detected using a conductivity detector. Subsequently, phosphate and silicate were analyzed based on derivatization with molybdate and spectrophotometry at 700 nm. The detection limits at S/N = 3 ranged from 0.11 to 2.9 µM for analyte ionic species. This method was applied to practical river water and wastewater with acceptable criteria for the anion-cation balance and comparisons of the measured and calculated electrical conductivity, demonstrating the usefulness of the present method for water quality monitoring.

Formulation design of ranitidine hydrochloride to reduce its moisture absorption characteristics.

PubMed

Khan, Shagufta; Giradkar, Praful; Yeole, Pramod

2009-01-01

This investigation examined the effect of a ranitidine hydrocholoride (RHCl)-ion exchange resin complexation on the drug's moisture uptake behavior. Drug resin complexes (DRCs) were prepared using the batch method with (i) two weak cation exchange resins, Polacrilex with exchangeable H+ and Polacrillin potassium; and (ii) a strong cation exchange resin;Sodium polystyrene sulfonate. RHCl, simple resins, and DRCs were subjected to storage stability under 40 +/- 2 degrees C and 75 +/- 5% relative humidity (RH) for 16 h, and the resulting percent increase in weight was calculated. DRCs gained less moisture than the simple drug and free resins. Out of the three complexes tested, DRC containing Polacrilex resin showed the most promising effect in protecting RHCl against moisture uptake with an increase in weight of 10.22 +/- 17% (free RHCl gained 28.11%) and was thereby selected for tablet formulation. Tablets were prepared using simple RHCl with Starch 1500 (F1); low moisture-grade Starch 1500 LM (F2); RHCl as DRC with Starch 1500 (F3); and, Starch 1500 LM (F4). Tablets were tested for equilibrium moisture content (EMC) under different humidity conditions and hygroscopicity in the presence and absence of light. In addition, stability studies were run over the duration of 6 months in conditions under 40 +/- 2 degrees C and 75 +/- 5% RH. The EMC of tablets at 80% RH decreased in the following order: F1 > F2 > marketed coated tablet > F3 > F4. The results of hygroscopicity testing revealed that both rate and extent of moisture gain in the presence or absence of light by F3 and F4 were significantly less than F1, F2, and marketed coated tablet (P < 0.05). Stability studies showed insignificant changes in weight, breaking force, friability, and disintegration time for tablets containing resin, while significant changes in these properties were found in tablets without resin. Thus, Polacrilex resin with exchangeable H+ was found to be the best for protecting RHCl against moisture uptake.

Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

PubMed Central

Binetti, Enrico; Striccoli, Marinella; Sibillano, Teresa; Giannini, Cinzia; Brescia, Rosaria; Falqui, Andrea; Comparelli, Roberto; Corricelli, Michela; Tommasi, Raffaele; Agostiano, Angela; Curri, M Lucia

2015-01-01

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices. PMID:27877842

Ion transport in the microporous titanosilicate ETS-10.

PubMed

Wei, Ta-Chen; Hillhouse, Hugh W

2006-07-20

Impedance spectroscopy was used to investigate ion transport in the microporous crystalline framework titanosilicate ETS-10 in the frequency range from 1 Hz to 10 MHz. These data were compared to measured data from the microporous aluminosilicate zeolite X. Na-ETS-10 was found to have a lower activation energy for ion conduction than that of NaX, 58.5 kJ/mol compared to 66.8 kJ/mol. However, the dc conductivity and ion hopping rate for Na-ETS-10 were also lower than NaX. This was found to be due to the smaller entropy contribution in Na-ETS-10 because of its high cation site occupancy. This was verified by ion exchanging Na(+) with Cu(2+) in both microporous frameworks. This exchange decreases the cation site occupancy and reduces correlation effects. The exchanged Cu-ETS-10 was found to have both lower activation energy and higher ionic conductivity than CuX. Zeolite X has the highest ion conductivity among the zeolites, and thus the data shown here indicate that ETS-10 has more facile transport of higher valence cations which may be important for ion-exchange, environmental remediation of radionucleotides, and nanofabrication.

Reducing the Cation Exchange Capacity of Lithium Clay to Form Better Dispersed Polymer-Clay Nanocomposites

NASA Technical Reports Server (NTRS)

Liang, Maggie

2004-01-01

Polymer-clay nanocomposites have exhibited superior strength and thermo- oxidative properties as compared to pure polymers for use in air and space craft; however, there has often been difficulty completely dispersing the clay within the matrices of the polymer. In order to improve this process, the cation exchange capacity of lithium clay is first lowered using twenty-four hour heat treatments of no heat, 130 C, 150 C, or 170 C to fixate the lithium ions within the clay layers so that they are unexchangeable. Generally, higher temperatures have generated lower cation exchange capacities. An ion exchange involving dodecylamine, octadecylamine, or dimethyl benzidine (DMBZ) is then employed to actually expand the clay galleries. X-ray diffraction and transmission electron microscopy can be used to determine whether the clay has been successfully exfoliated. Finally, resins of DMBZ with clay are then pressed into disks for characterization using dynamic mechanical analyzer and oven- aging techniques in order to evaluate their glass transition, modulus strength, and thermal-oxidative stability in comparison to neat DMBZ. In the future, they may also be tested as composites for flexural and laminar shear strength.

Tackling capacity fading in vanadium flow batteries with amphoteric membranes

NASA Astrophysics Data System (ADS)

Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

2017-11-01

Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

Interactions among K+-Ca2+ exchange, sorption of m-dinitrobenzene, and smectite quasicrystal dynamics.

PubMed

Chatterjee, Ritushree; Laird, David A; Thompson, Michael L

2008-12-15

The fate of organic contaminants in soils and sediments is influenced by sorption of the compounds to surfaces of soil materials. We investigated the interaction among sorption of an organic compound, cation exchange reactions, and both the size and swelling of smectite quasicrystals. Two reference smectites that vary in location and amount of layer charge, SPV (a Wyoming bentonite) and SAz-1 were initially Ca- and K-saturated and then equilibrated with mixed 0.01 M KCl and 0.005 M CaCl2 salt solutions both with and without the presence of 200 mg L(-1) m-dinitrobenzene (m-DNB). In general, sorption of m-DNB increased with the amount of K+ in the system for both clays, and the SPV sorbed more m-DNB than the SAz-1. Sorption of m-DNB increased the preference of Ca-SPV for K+ relative to Ca2+ but had little effect on K+-Ca2+ selectivity for K-SPV. Selectivity for K+ relative to Ca2+ was slightly higher for both K-SAz-1 and Ca-SAz-1 in the presence of m-DNB than in its absence. Distinct hysteresis loops were observed for the K+-Ca2+ cation exchange reactions for both clays, and the legacy of having been initially Ca- or K-saturated influenced sorption of m-DNB by SPV but had little effect for SAz-1. Suspension X-ray diffraction was used to measure changes in d-spacing and the relative thickness of smectite quasicrystals during the cation exchange and m-DNB sorption reactions. The results suggest that interactions among cation exchange and organic sorption reactions are controlled byan inherently hysteretic complex feedback process that is regulated by changes in the size and extent of swelling of smectite quasicrystals.

Intercalated layered clay composites and their applications

NASA Astrophysics Data System (ADS)

Phukan, Anjali

Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double or pseudo-trilayer composites. Metal ion and metal ion metal salts intercalated on Montmorillonite are efficient catalysts for Friedel-Crafts (FC) reactions, such as benzylation of benzene, synthesis of Raspberry ketone [4-(4'-hydroxyphenyl)butan-2-one] etc. Montmorillonite clay can be used as a good support for controlled release of pesticides and medicinal drugs, adsorbent for cationic dyes, toxic substances and heavy metals effective adsorbent for radioactive and toxic industrial wastes,...

Li interactions with the B40 fullerene and its application in Li-ion batteries: DFT studies

NASA Astrophysics Data System (ADS)

Moradi, Morteza; Bagheri, Zargham; Bodaghi, Ali

2017-05-01

The interaction of Li and Li+ with a B40 all-boron fullerene was theoretically investigated at the B3LYP, and Minnesota 2006 levels of theory. It was found that, unexpectedly, the interaction Li+ cation with the electron deficient B40 fullerene is stronger than the Li atom. It indicates that the B40 fullerene does not act as a conventional Lewis acid because of its highly correlated structure. Frontier molecular orbitals, partial density of states, and natural bond orbital analyses were used to discuss this unusual behavior. Our calculations indicate that this behavior makes the B40 fullerene more appropriate for application in the Li-ion batteries as anode material. The calculated cell voltage is about 530 mV. Also, it was found that Hartree Fock (HF) exchange percentage of density functionals has a reverse effect on the adsorption energies of Li and Li+. This energy is increased and decreased, respectively, for Li+ and Li adsorptions by increasing %HF exchange. Finally, a potential energy surface for Li and Li+ penetration into B40 fullerene was predicted.

Crystal structure and cation exchanging properties of a novel open framework phosphate of Ce (IV)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bevara, Samatha; Achary, S. N., E-mail: sachary@barc.gov.in; Tyagi, A. K.

2016-05-23

Herein we report preparation, crystal structure and ion exchanging properties of a new phosphate of tetravalent cerium, K{sub 2}Ce(PO{sub 4}){sub 2}. A monoclinic structure having framework type arrangement of Ce(PO{sub 4}){sub 6} units formed by C2O{sub 8} square-antiprism and PO{sub 4} tetrahedra is assigned for K{sub C}e(PO{sub 4}){sub 2}. The K{sup +} ions are occupied in the channels formed by the Ce(PO{sub 4})6 and provide overall charge neutrality. The unique channel type arrangements of the K+ make them exchangeable with other cations. The ion exchanging properties of K2Ce(PO4)2 has been investigated by equilibrating with solution of 90Sr followed by radiometricmore » analysis. In optimum conditions, significant exchange of K+ with Sr2+ with Kd ~ 8000 mL/g is observed. The details of crystal structure and ion exchange properties are explained and a plausible mechanism for ion exchange is presented.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aubart, M.A.; Dor Koch, J.F.; Pignolet, L.H.

The authors developed a homogeneous catalytic system for exchange of deuterium onto water. Platinum-gold phosphine cations catylze this exchange in pyridine. The authors probed these reactions kinetically and studied the catalysts by NMR allowing them to propose a reaction mechanism.

Concentration of perrhenate and pertechnetate solutions

DOEpatents

Knapp, F.F.; Beets, A.L.; Mirzadeh, S.; Guhlke, S.

1998-03-17

A method is described for preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: (a) providing a generator column loaded with a composition containing a parent radioisotope; (b) eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate; (c) eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; (d) eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and (e) eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution. 1 fig.

Concentration of perrhenate and pertechnetate solutions

DOEpatents

Knapp, Furn F.; Beets, Arnold L.; Mirzadeh, Saed; Guhlke, Stefan

1998-01-01

A method of preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: a. providing a generator column loaded with a composition containing a parent radioisotope; b. eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate. c. eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; d. eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and e. eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution.

A Simplified Representation of the Chemical Nature and Reactions of Soil Humus.

ERIC Educational Resources Information Center

Stevenson, F. J.; Olsen, R. A.

1989-01-01

Presented is a comprehensible structural representation of humic substances. A number of important roles of soil organic matter, including contribution to the cation-exchange capacity, binding of pesticides, and formation of complexes with micronutrient cations, are illustrated. (Author/CW)

Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

NASA Astrophysics Data System (ADS)

Cole, David R.

2000-03-01

Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order clearly reflects the influence of the change in cation chemistry, i.e., Ba > Sr > Ca. A similar pattern is observed for the layer silicate-H 2O systems, where chlorite>biotite>muscovite. The link between cation chemistry and rate is more complicated in this case, but in general, the order follows a trend where Mg-Fe > K-Mg > K, with an associated increase in Si and Al, and decrease in hydroxyl. The isotopic-chemical relations suggest that oxygen isotope exchange behavior monitored experimentally in this study is the net result of bond-breaking and dissolution of the mineral, complex ion formation in solution and growth of the mineral, whose structure is controlled, in large part, by the lattice energy. We compared the rates against the electrostatic attractive lattice energies (neglecting the repulsive forces), normalized per number of cations. The correlations between rates and lattice energies are quite good for both mineral-H 2O systems. The increase in rates correlated with a decrease in the electrostatic attractive lattice energies, i.e., the greater the lattice energy required to break up the crystal, the more sluggish the rates for both chemical and isotopic exchange. By establishing an unambiguous relationship between rate, lattice energy, and ultimately temperature, we can begin to develop empirical equations useful in predicting rates of isotopic exchange for minerals for which experimental data are lacking.

Removal of diphenhydramine from water by swelling clay minerals.

PubMed

Li, Zhaohui; Chang, Po-Hsiang; Jiang, Wei-Teh; Jean, Jiin-Shuh; Hong, Hanlie; Liao, Libing

2011-08-01

Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities. Copyright © 2011 Elsevier Inc. All rights reserved.

Cation-exchanged zeolites for the selective oxidation of methane to methanol

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira; ...

2017-10-19

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

Cation-exchanged zeolites for the selective oxidation of methane to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

Extraction of Carbon Dioxide and Hydrogen from Seawater By an Electrolytic Cation Exchange Module (E-CEM) Part 5: E-CEM Effluent Discharge Composition as a Function of Electrode Water Composition

DTIC Science & Technology

2017-08-01

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6360--17-9743 Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrolytic...Cation Exchange Module (E-CEM) Part V: E-CEM Effluent Discharge Composition as a Function of Electrode Water Composition August 1, 2017 Approved for...Office of Naval Research Arlington, Virginia Dennis r. HarDy Nova Research Inc. Alexandria, Virginia i REPORT DOCUMENTATION PAGE Form

Two cation exchange models for direct and inverse modelling of solution major cation composition in equilibrium with illite surfaces

NASA Astrophysics Data System (ADS)

Tournassat, Christophe; Gailhanou, Hélène; Crouzet, Catherine; Braibant, Gilles; Gautier, Anne; Lassin, Arnault; Blanc, Philippe; Gaucher, Eric C.

2007-03-01

Na/K, Na/Ca and Na/Mg exchange isotherms were performed on the fine fraction (<2 μm) of Imt-2 illite samples at a total normality of about 0.005 mol/L in anionic chloride medium. The derived selectivity coefficients for Na/K, Na/Ca and Na/Mg were found to vary as a function of the exchanger composition and compared well with the data collected in the literature for similar experimental conditions. Two models were built to reproduce the data: the first was a multi(2)-site model with constant Gaines and Thomas selectivity coefficients; the second was a one-site model taking into account surface species activity coefficients. The results of the models were in rather good agreement with both our data and literature data. The multi-site model proved to be efficient in predicting the exchanger composition as a function of the Na/Ca/Mg/K concentrations in solution, whereas the one-site model proved to be a better approach to derive the Na/Ca/Mg/K concentrations in solution based on the knowledge of the exchanger composition and the total normality of the solution. The interest of this approach is illustrated by the need for major cation solute concentration predictions in compacted clay for the characterization of nuclear deep disposal host rock repositories.

Interaction of ammonium with birnessite: Evidence of a chemical and structural transformation in alkaline aqueous medium

NASA Astrophysics Data System (ADS)

Boumaiza, Hella; Coustel, Romain; Despas, Christelle; Ruby, Christian; Bergaoui, Latifa

2018-02-01

The ammonium cation interaction with Na-birnessite in aqueous alkaline medium was studied. Solution and solid analysis give evidence that birnessite is not only acting as a cationic exchanger toward NH4+. The surface analysis performed by XPS showed that N1s spectra are characterized by the existence of two different environments: one assignable to an interlayer NH4+ and the second to a chemisorbed N-species. Structural and chemical transformations were observed on birnessite with nitrogen mass balance deficit. The monitoring of NH4+, Na+, Mn2+, NO3- and NO2- and solid changes (average oxidation state of Mn, cation exchange capacity, solid nitrogen content and symmetry evolution identified by XRD and FTIR) indicate unambiguously that NH4+ reacts chemically with the birnessite.

Clay-catalyzed reactions of coagulant polymers during water chlorination

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Lee, C.-K.; Chao, H.-P.; Peng, C.-L.; Chiou, C.T.

2004-01-01

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

NASA Astrophysics Data System (ADS)

Lee, Min-Hong

The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on the length of the alkyl chain. Although introduced mesopores alleviated the limited reagent diffusion to reactive sites due to the microporosity of the NaX zeolites, no marked improvement in the product yields was achieved with either the 1-chloroalkanes or the trialkyl phosphates test compounds, regardless of alkyl chain length. The disappointing results have been attributed to lack of substantial net increase in the numbers of zeolite nucleophilic sites accompanying mesopore introduction.

CATION TRANSPORT AND PARTITIONING DURING A FIELD TEST OF ELECTROOSMOSIS

EPA Science Inventory

Field experiments were conducted to evaluate the effects of soil properties, such as the cation exchange capacity and mineral content, on pH, soluble ion concentrations, and electrical conductivity during electroosmosis in a silty clay soil. The soil is composed mainly of quartz ...

Simultaneous determination of inorganic anions and cations in explosive residues by ion chromatography.

PubMed

Meng, Hong-Bo; Wang, Tian-Ran; Guo, Bao-Yuan; Hashi, Yuki; Guo, Can-Xiong; Lin, Jin-Ming

2008-07-15

A non-suppressed ion chromatographic method by connecting anion-exchange and cation-exchange columns directly was developed for the separation and determination of five inorganic anions (sulfate, nitrate, chloride, nitrite, and chlorate) and three cations (sodium, ammonium, and potassium) simultaneously in explosive residues. The mobile phase was composed of 3.5mM phthalic acid with 2% acetonitrile and water at flow rate of 0.2 mL/min. Under the optimal conditions, the eight inorganic ions were completely separated and detected simultaneously within 16 min. The limits of detection (S/N=3) of the anions and cations were in the range of 50-100 microg/L and 150-320 microg/L, respectively, the linear correlation coefficients were 0.9941-0.9996, and the R.S.D. of retention time and peak area were 0.10-0.29% and 5.65-8.12%, respectively. The method was applied successfully to the analysis of the explosive samples with satisfactory results.

Probing dynamics and mechanism of exchange process of quaternary ammonium dimeric surfactants, 14-s-14, in the presence of conventional surfactants.

PubMed

Liu, Jun; Jiang, Yan; Chen, Hong; Mao, Shi Zhen; Du, You Ru; Liu, Mai Li

2012-12-27

In this Article, we investigated effects of different types of conventional surfactants on exchange dynamics of quaternary ammonium dimeric surfactants, with chemical formula C(14)H(29)N(+)(CH(3))(2)- (CH(2))(s)-N(+)(CH(3))(2)C(14)H(29)·2Br(-), or 14-s-14 for short. Two nonionic surfactants, TritonX-100 (TX-100) and polyethylene glycol (23) laurylether (Brij-35), and one cationic surfactant, n-tetradecyltrimethyl ammonium bromide (TTAB), and one ionic surfactant, sodium dodecyl sulfate (SDS) were chosen as typical conventional surfactants. Exchange rates of 14-s-14 (s = 2, 3, and 4) between the micelle form and monomer in solution were detected by two NMR methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). Results show that the nonionic surfactants (TX-100 and Brij-35), the cationic surfactant (TTAB), and the ionic surfactant (SDS) respectively accelerated, barely influenced, and slowed the exchange rate of 14-s-14. The effect mechanism was investigated by the self-diffusion experiment, relaxation time measurements (T(2)/T(1)), the fluorescence experiment (I(1)/I(3)) and observed chemical shift variations. Results reveal that, nonionic conventional surfactants (TX-100 and Brij-35) loosened the molecule arrangement and decreased hydrophobic interactions in the micelle, and thus accelerated the exchange rate of 14-s-14. The cationic conventional surfactant (TTAB) barely changed the molecule arrangement and thus barely influenced the exchange rate of 14-s-14. The ionic conventional surfactant (SDS) introduced the electrostatic attraction effect, tightened the molecule arrangement, and increased hydrophobic interactions in the micelle, and thus slowed down the exchange rate of 14-s-14. Additionally, the two-step exchange mechanism of 14-s-14 in the mixed solution was revealed through interesting variation tendencies of exchange rates of 14-s-14.

A comparative study of chelating and cationic ion exchange resins for the removal of palladium(II) complexes from acidic chloride media.

PubMed

Hubicki, Zbigniew; Wołowicz, Anna

2009-05-30

The increasing demand for palladium for technological application requires the development of ion exchange chromatography. Recently ion exchange chromatography has developed largely as a result of new types of ion exchangers available on the market of which two types are widely applied. One of them are selective (chelating) and modified ion exchangers and the other one are liquid exchangers. Two types of ion exchange resins such as chelating (Lewatit TP 214, Purolite S 920) and cationic (Chelite S, Duolite GT 73) ion exchangers are used for the recovery of palladium(II) complexes from chloride media (0.1-2.0M HCl-1.0M NaCl-0.0011 M Pd(II); 0.1-2.0M HCl-2.0M NaCl-0.0011M Pd(II)). The influence of concentration of hydrochloric acid, sodium chloride as well as the phase contact time on the degree of recovery of palladium(II) complexes was studied. Moreover, the amount of palladium(II) chlorocomplexes sorbed onto ion exchangers, the working ion exchange capacities and the weight and bed distribution coefficients were calculated in order to judge which of two types of resins possesses the best performance towards palladium(II) complexes.

Electrochromatographic retention of peptides on strong cation-exchange stationary phases.

PubMed

Nischang, Ivo; Höltzel, Alexandra; Tallarek, Ulrich

2010-03-01

We analyze the systematic and substantial electrical field-dependence of electrochromatographic retention for four counterionic peptides ([Met5]enkephalin, oxytocin, [Arg8]vasopressin, and luteinizing hormone releasing hormone (LHRH) ) on a strong cation-exchange (SCX) stationary phase. Our experiments show that retention behavior in the studied system depends on the charge-selectivity of the stationary phase particles, the applied voltage, and the peptides' net charge. Retention factors of twice positively charged peptides ([Arg8]vasopressin and LHRH at pH 2.7) decrease with increasing applied voltage, whereas lower charged peptides (oxytocin and [Met5]enkephalin at pH 2.7, [Arg8]vasopressin and LHRH at pH 7.0) show a concomitant increase in their retention factors. The observed behavior is explained on the basis of electrical field-induced concentration polarization (CP) that develops around the SCX particles of the packing. The intraparticle concentration of charged species (buffer ions, peptides) increases with increasing applied voltage due to diffusive backflux from the enriched CP zone associated with each SCX particle. For twice charged and on the SCX phase strongly retained peptides the local increase in mobile phase ionic strength reduces the electrostatic interactions with the stationary phase, which explains the decrease of retention factors with increasing applied voltage and CP intensity. Lower charged and weaker retained peptides experience a much stronger relative intraparticle enrichment than the twice-charged peptides, which results in a net increase of retention factors with increasing applied voltage. The CP-related contribution to electrochromatographic retention of peptides on the SCX stationary phase is modulated by the applied voltage, the mobile phase ionic strength, and the peptides' net charge and could be used for selectivity tuning in difficult separations.

Alkaline degradation studies of anion exchange polymers to enable new membrane designs

NASA Astrophysics Data System (ADS)

Nunez, Sean Andrew

Current performance targets for anion-exchange membrane (AEM) fuel cells call for greater than 95% alkaline stability for 5000 hours at temperatures up to 120 °C. Using this target temperature of 120 °C, an incisive 1H NMR-based alkaline degradation method to identify the degradation products of n-alkyl spacer tetraalkylammonium cations in various AEM polymers and small molecule analogs. Herein, the degradation mechanisms and rates of benzyltrimethylammonium-, n-alkyl interstitial spacer- and n-alkyl terminal pendant-cations are studied on several architectures. These findings demonstrate that benzyltrimethylammonium- and n-alkyl terminal pendant cations are more labile than an n-alkyl interstitial spacer cation and conclude that Hofmann elimination is not the predominant mechanism of alkaline degradation. Additionally, the alkaline stability of an n-alkyl interstitial spacer cation is enhanced when combined with an n-alkyl terminal pendant. Interestingly, at 120 °C, an inverse trend was found in the overall alkaline stability of AEM poly(styrene) and AEM poly(phenylene oxide) samples than was previously shown at 80 °C. Successive small molecule studies suggest that at 120 °C, an anion-induced 1,4-elimination degradation mechanism may be activated on styrenic AEM polymers bearing an acidic alpha-hydrogen. In addition, an ATR-FTIR based method was developed to assess the alkaline stability of solid membranes and any added resistance to degradation that may be due to differential solubilities and phase separation. To increase the stability of anion exchange membranes, Oshima magnesate--halogen exchange was demonstrated as a method for the synthesis of new anion exchange membranes that typically fail in the presence of organolithium or Grignard reagents alone. This new chemistry, applied to non-resinous polymers for the first time, proved effective for the n-akyl interstitial spacer functionalization of poly(phenylene oxide) and poly(styrene- co-ethylene-co-butylene-co-styrene) polymer backbones. The comprehensive methodologies for the assessment of alkaline stability in AEMs as well as the new synthetic methodologies are intended as a guide toward robust AEM synthetic designs that approach current performance standards.

Modeling and simulation of protein elution in linear pH and salt gradients on weak, strong and mixed cation exchange resins applying an extended Donnan ion exchange model.

PubMed

Wittkopp, Felix; Peeck, Lars; Hafner, Mathias; Frech, Christian

2018-04-13

Process development and characterization based on mathematic modeling provides several advantages and has been applied more frequently over the last few years. In this work, a Donnan equilibrium ion exchange (DIX) model is applied for modelling and simulation of ion exchange chromatography of a monoclonal antibody in linear chromatography. Four different cation exchange resin prototypes consisting of weak, strong and mixed ligands are characterized using pH and salt gradient elution experiments applying the extended DIX model. The modelling results are compared with the results using a classic stoichiometric displacement model. The Donnan equilibrium model is able to describe all four prototype resins while the stoichiometric displacement model fails for the weak and mixed weak/strong ligands. Finally, in silico chromatogram simulations of pH and pH/salt dual gradients are performed to verify the results and to show the consistency of the developed model. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of ionophores on the rate of intramolecular cation exchange in durosemiquinone ion pairs

NASA Technical Reports Server (NTRS)

Eastman, M. P.; Bruno, G. V.; Mcguyer, C. A.; Gutierrez, A. R.; Shannon, J. M.

1979-01-01

The effects of the ionophores 15-crown-5 (15C5), 18-crown-6 (18C6), dibenzo-18-crown-6 (DBC) and cryptand 222 (C222) on intramolecular cation exchange in ion pairs of the sodium salt of the durosemiquinone anion in benzene solution are investigated. Electron paramagnetic resonance spectra of the 18C6 and 15C5 complexes with durosemiquinone reduced by contact with a sodium mirror show an alternating line width which indicates that the sodium ion is being exchanged between equivalent sites near the oxygens of the semiquinone with activation energies of 8.7 and 6.0 kcal/mole and Arrhenius preexponential factors of 9 x 10 to the 12th/sec and 10 to the 12th/sec, respectively. Spectra obtained for the DBC complexes show no evidence of exchange, while those of C222 indicate rapid exchange. It is also noted that the hyperfine splitting constants measured do not change over the 50-K temperature interval studied.

Separation of aliphatic carboxylic acids and benzenecarboxylic acids by ion-exclusion chromatography with various cation-exchange resin columns and sulfuric acid as eluent.

PubMed

Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae-Jeong; Lee, Kwang-Pill

2003-05-16

The application of various hydrophilic cation-exchange resins for high-performance liquid chromatography (sulfonated silica gel: TSKgel SP-2SW, carboxylated silica gel: TSKgel CM-2SW, sulfonated polymethacrylate resin: TSKgel SP-5PW, carboxylated polymethacrylate resins: TSKgel CM-5PW and TSKgel OA-Pak A) as stationary phases in ion-exclusion chromatography for C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, butyric, isovaleric, valeric, isocaproic, caproic, 2-methylhexanoic and heptanoic acids) and benzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic, salicylic acids and phenol) was carried out using diluted sulfuric acid as the eluent. Silica-based cation-exchange resins (TSKgel SP-2SW and TSKgel CM-2SW) were very suitable for the ion-exclusion chromatographic separation of these benzenecarboxylic acids. Excellent simultaneous separation of these benzenecarboxylic acids was achieved on a TSKgel SP-2SW column (150 x 6 mm I.D.) in 17 min using a 2.5 mM sulfuric acid at pH 2.4 as the eluent. Polymethacrylate-based cation-exchange resins (TSKgel SP-5PW, TSKgel CM-5PW and TSKgel OA-Pak A) acted as advanced stationary phases for the ion-exclusion chromatographic separation of these C1-C7 aliphatic carboxylic acids. Excellent simultaneous separation of these C1-C7 acids was achieved on a TSKgel CM-5PW column (150 x 6 mm I.D.) in 32 min using a 0.05 mM sulfuric acid at pH 4.0 as the eluent.

Double-membrane triple-electrolyte redox flow battery design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yushan, Yan; Gu, Shuang; Gong, Ke

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers greatmore » freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.« less

Process for separation and preconcentration of radium from water

DOEpatents

Dietz, Mark; Horwitz, E. Philip; Chiarizia, Renato; Bartsch, Richard A.

1999-01-01

A process for preconcentrating and separating radium from a contaminated solution containing at least water and radium includes the steps of adding a quantity of a water-soluble macrocyclic polyether to the contaminated solution to form a combined solution. An acid is added to the combined solution to form an acidic combined solution having an ›H.sup.+ ! concentration of about 0.5M. The acidic combined solution is contacted with a sulfonic acid-based strong acid cation exchange medium or a organophilic sulfonic acid medium having a plurality of binding sites thereon to bind the radium thereto and to form a radium-depleted solution. The radium-depleted solution is separated from the strong acid cation exchange medium or organophilic sulfonic acid medium. The radium remaining bound to the exchange medium or organophilic reagent is then stripped from the exchange medium or organophilic medium and the activity of the radium is measured.

Process for separation and preconcentration of radium from water

DOEpatents

Dietz, M.; Horwitz, E.P.; Chiarizia, R.; Bartsch, R.A.

1999-01-26

A process for preconcentrating and separating radium from a contaminated solution containing at least water and radium includes the steps of adding a quantity of a water-soluble macrocyclic polyether to the contaminated solution to form a combined solution. An acid is added to the combined solution to form an acidic combined solution having an [H{sup +}] concentration of about 0.5M. The acidic combined solution is contacted with a sulfonic acid-based strong acid cation exchange medium or a organophilic sulfonic acid medium having a plurality of binding sites thereon to bind the radium thereto and to form a radium-depleted solution. The radium-depleted solution is separated from the strong acid cation exchange medium or organophilic sulfonic acid medium. The radium remaining bound to the exchange medium or organophilic reagent is then stripped from the exchange medium or organophilic medium and the activity of the radium is measured. 24 figs.

Removal of Carbon Dioxide from Gas Mixtures Using Ion-Exchanged Silicoaluminophosphates

NASA Technical Reports Server (NTRS)

Hernandez-Maldonado, Arturo J (Inventor); Rivera-Ramos, Milton E (Inventor); Arevalo-Hidalgo, Ana G (Inventor)

2017-01-01

Na+-SAPO-34 sorbents were ion-exchanged with several individual metal cations for CO2 absorption at different temperatures (273-348 K) and pressures (<1 atm). In general, the overall adsorption performance of the exchanged materials increased as follows: Ce3+

Exchangers man the pumps: Functional interplay between proton pumps and proton-coupled Ca(2+) exchangers

USDA-ARS?s Scientific Manuscript database

Tonoplast-localised proton-coupled Ca(2+) transporters encoded by cation/H(+) exchanger (CAX) genes play a critical role in sequestering Ca(2+) into the vacuole. These transporters may function in coordination with Ca(2+) release channels, to shape stimulus-induced cytosolic Ca(2+) elevations. Recen...

Landscape determinants of exchangeable calcium and magnesium in Ozark Highland forest soils

Treesearch

John M. Kabrick; Keith W. Goyne; Zhaofei Fan; Dennis Meinert

2011-01-01

Exchangeable base cations, particularly Ca and Mg, largely govern soil acidity and, consequently, plant species composition in temperate forests. Although studies have identified soil and terrain characteristics affecting exchangeable Ca and Mg, few studies have identified the relative importance of factors affecting Ca and Mg distribution across landscapes. Objectives...

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

NASA Astrophysics Data System (ADS)

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

PubMed Central

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-01-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g−1) and large pore volumes (up to 0.90 cm3 g−1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4′-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405−; the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane. PMID:26062725

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers.

PubMed

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-11

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m(2) g(-1)) and large pore volumes (up to 0.90 cm(3) g(-1)). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4'-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O40(5-); the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

SEPARATION PROCESS USING COMPLEXING AND ADSORPTION

DOEpatents

Spedding, J.H.; Ayers, J.A.

1958-06-01

An adsorption process is described for separating plutonium from a solution of neutron-irradiated uranium containing ions of a compound of plutonium and other cations. The method consists of forming a chelate complex compound with plutoniunn ions in the solution by adding a derivative of 8- hydroxyquinoline, which derivative contains a sulfonic acid group, and adsorbing the remaining cations from the solution on a cation exchange resin, while the complexed plutonium remains in the solution.

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

PubMed

Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2016-08-01

The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

Selective digestion of Ba2+/Ca2+ alginate gel microdroplets for single-cell handling

NASA Astrophysics Data System (ADS)

Odaka, Masao; Hattori, Akihiro; Matsuura, Kenji; Yasuda, Kenji

2018-06-01

Cells encapsuled by polymer microdroplets are an effective platform for the identification and separation of individual cells for single-cell-based analysis. However, a key challenge is to maintain and release the captured cells in the microdroplets selectively, nondestructively, and noninvasively. We developed a simple method of encapsulating cells in alginate microdroplets having different digestion characteristics. Cells were diluted with an alginate polymer of sol state and encapsulated into microdroplets with Ba2+ and Ca2+ by a spray method. When a chelating buffer was applied, alginate gel microdroplets were digested according to the difference in chelating efficiency of linkage-divalent cations; hence, two types of alginate microdroplets were formed. Moreover, we examined the capability of the alginate gel to exchange linkage-divalent cations and found that both Ca2+ exchange in Ba-alginate microdroplets and Ba2+ exchange in Ca-alginate microdroplets occurred. These results indicate that the potential applications of a mixture of alginate microdroplets with different divalent cations control the selective digestion of microdroplets to improve the high-throughput, high-content microdroplet-based separation, analysis, or storage of single cells.

Precipitation-mediated responses of soil acid buffering capacity to long-term nitrogen addition in a semi-arid grassland

NASA Astrophysics Data System (ADS)

Cai, Jiangping; Luo, Wentao; Liu, Heyong; Feng, Xue; Zhang, Yongyong; Wang, Ruzhen; Xu, Zhuwen; Zhang, Yuge; Jiang, Yong

2017-12-01

Atmospheric nitrogen (N) deposition can result in soil acidification and reduce soil acid buffering capacity. However, it remains poorly understood how changes in precipitation regimes with elevated atmospheric N deposition affect soil acidification processes in a water-limited grassland. Here, we conducted a 9-year split-plot experiment with water addition as the main factor and N addition as the second factor. Results showed that soil acid buffering capacity significantly decreased with increased N inputs, mainly due to the decline of soil effective cation exchange capacity (ECEC) and exchangeable basic cations (especially Ca2+), indicating an acceleration of soil acidification status in this steppes. Significant interactive N and water effects were detected on the soil acid buffering capacity. Water addition enhanced the soil ECEC and exchangeable base cations and thus alleviated the decrease of soil acid buffering capacity under N addition. Our findings suggested that precipitation can mitigate the impact of increased N deposition on soil acidification in semi-arid grasslands. This knowledge should be used to improve models predicting soil acidification processes in terrestrial ecosystems under changing environmental conditions.

Quality improvement of acidic soils by biochar derived from renewable materials.

PubMed

Moon, Deok Hyun; Hwang, Inseong; Chang, Yoon-Young; Koutsospyros, Agamemnon; Cheong, Kyung Hoon; Ji, Won Hyun; Park, Jeong-Hun

2017-02-01

Biochar derived from waste plant materials and agricultural residues was used to improve the quality of an acidic soil. The acidic soil was treated for 1 month with both soy bean stover-derived biochar and oak-derived biochar in the range of 1 to 5 wt% for pH improvement and exchangeable cation enhancement. Following 1 month of treatment, the soil pH was monitored and exchangeable cations were measured. Moreover, a maize growth experiment was performed for 14 days with selected treated soil samples to confirm the effectiveness of the treatment. The results showed that the pH of the treated acidic soil increased by more than 2 units, and the exchangeable cation values were greatly enhanced upon treatment with 5 wt% of both biochars, after 1 month of curing. Maize growth was superior in the 3 wt% biochar-treated samples compared to the control sample. The presented results demonstrate the effective use of biochar derived from renewable materials such as waste plant materials and agricultural residues for quality improvement of acidic soils.

Choices of capture chromatography technology in antibody manufacturing processes.

PubMed

DiLeo, Michael; Ley, Arthur; Nixon, Andrew E; Chen, Jie

2017-11-15

The capture process employed in monoclonal antibody downstream purification is not only the most critically impacted process by increased antibody titer resulting from optimized mammalian cell culture expression systems, but also the most important purification step in determining overall process throughput, product quality, and economics. Advances in separation technology for capturing antibodies from complex feedstocks have been one focus of downstream purification process innovation for past 10 years. In this study, we evaluated new generation chromatography resins used in the antibody capture process including Protein A, cation exchange, and mixed mode chromatography to address the benefits and unique challenges posed by each chromatography approach. Our results demonstrate the benefit of improved binding capacity of new generation Protein A resins, address the concern of high concentration surge caused aggregation when using new generation cation exchange resins with over 100mg/mL binding capacity, and highlight the potential of multimodal cation exchange resins for capture process design. The new landscape of capture chromatography technologies provides options to achieve overall downstream purification outcome with high product quality and process efficiency. Copyright © 2017 Elsevier B.V. All rights reserved.

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

PubMed

Tanaka, Kazuhiko; Mori, Masanobu; Xu, Qun; Helaleh, Murad I H; Ikedo, Mikaru; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Fritz, James S; Haddad, Paul R

2003-05-16

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

Suppressing Shuttle Effect Using Janus Cation Exchange Membrane for High-Performance Lithium-Sulfur Battery Separator.

PubMed

Li, Zhen; Han, Yu; Wei, Junhua; Wang, Wenqiang; Cao, Tiantian; Xu, Shengming; Xu, Zhenghe

2017-12-27

Suppressing the shuttle effect of polysulfide ions to obtain high durability and good electrochemical performance is of great concern in the field of lithium-sulfur batteries. To address this issue, a Janus membrane consisting of an ultrathin dense layer and a robust microporous layer is fabricated using cation exchange resin. Different from the composite membranes made from polyolefin membranes, the multiple layers of the Janus membrane in this study are synchronously generated by one step, getting rid of the additional complex coating processes. Excellent overall performance is obtained by the cooperation of multiple factors. The excellent ionic selectivity of cation exchange resin renders a great suppression of the shuttle effect, endowing the lithium-sulfur battery with high Coulombic efficiency of 92.0-99.0% (LiNO 3 -free electrolyte). The ultrathin property of a dense layer renders a low ionic resistance, resulting in 60% higher discharge capacity over the entire C-rates (versus the control sample with Celgard 2400 membrane). The robust macroporous layer supports the ultrathin layer to achieve a free-standing property, ensuring the usability of the Janus membrane.

Evaluation of the removal of Strontium-90 from groundwater using a zeolite rich-rock permeable treatment wall

NASA Astrophysics Data System (ADS)

Seneca, S. M.; Rabideau, A. J.; Bandilla, K.

2010-12-01

Experimental and modeling studies are in progress to evaluate the long-term performance of a permeable treatment wall comprised of zeolite-rich rock for the removal of strontium-90 from groundwater. Multiple column tests were performed at the University at Buffalo and on-site West Valley Environmental Services; columns were supplied with synthetic groundwater referenced to anticipate field conditions and radioactive groundwater on-site WVES. The primary focus in this work is on quantifying the competitive ion exchange among five cations (Na+, K+, Ca2+, Mg2+, and Sr2+); the data obtained from the column studies is used to support the robust estimation of zeolite cation exchange parameters. This research will produce a five-solute cation exchange model describing the removal efficiency of the zeolite, using the various column tests to calibrate and validate the geochemical transport model. The field-scale transport model provides flexibility to explore design parameters and potential variations in groundwater geochemistry to investigate the long-term performance of a full scale treatment wall at the Western New York nuclear facility.

B-Site Metal Cation Exchange in Halide Perovskites

DOE PAGES

Eperon, Giles E.; Ginger, David S.

2017-05-02

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

B-Site Metal Cation Exchange in Halide Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eperon, Giles E.; Ginger, David S.

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

PubMed Central

Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

2016-01-01

Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

Interaction between tetracycline and smectite in aqueous solution.

PubMed

Li, Zhaohui; Chang, Po-Hsiang; Jean, Jiin-Shuh; Jiang, Wei-Teh; Wang, Chih-Jen

2010-01-15

The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d(001) spacing. The TC adsorption capacity was equivalent to 0.74-1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H(+), resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H(+) resulted in the ratio of H(+) adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H(+) could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H(+) adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.

Tree species affect cation exchange capacity (CEC) and cation binding properties of organic matter in acid forest soils.

PubMed

Gruba, Piotr; Mulder, Jan

2015-04-01

Soil organic matter (SOM) in forest soil is of major importance for cation binding and acid buffering, but its characteristics may differ among soils under different tree species. We investigated acidity, cation exchange properties and Al bonding to SOM in stands of Scots pine, pedunculate oak, Norway spruce, European beech and common hornbeam in southern Poland. The content of total carbon (Ct) was by far the major contributor to total cation exchange capacity (CECt) even in loamy soils and a strong relationship between Ct and CECt was found. The slope of the regression of CECt to Ct increased in the order hornbeam≈oak

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

DOE PAGES

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

2016-06-13

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Chapter 3: Soil Chemistry

Treesearch

Jennifer D. Knoepp; Leonard F. DeBano; Daniel G. Neary

2005-01-01

The chemical properties of the soil that are affected by fire include individual chemical characteristics, chemical reactions, and chemical processes (DeBano and others 1998). The soil chemical characteristics most commonly affected by fire are organic matter, carbon (C), nitrogen (N), phosphorus (P), sulfur (S), cations, cation exchange capacity, pH, and buffer power...

The role of CAX1 and CAX3 in elemental distribution and abundance in Arabidopsis seed

USDA-ARS?s Scientific Manuscript database

The ability to alter nutrient partitioning within plant cells is poorly understood. In Arabidopsis (Arabidopsis thaliana), a family of endomembrane cation exchangers (CAXs) transports Ca(2+) and other cations. However, experiments have not focused on how the distribution and partitioning of calcium ...

Synthesis, characterization and applications of a new cation exchanger tamarind sulphonic acid (TSA) resin.

PubMed

Singh, A V; Sharma, Naresh Kumar; Rathore, Abhay S

2012-01-01

A new composite cation exchanger, tamarind sulphonic acid (TSA) resin has been synthesized. The chemically modified TSA ion exchange resin has been used for the removal and preconcentration of Zn2+, Cd2+, Fe2+, Co2+ and Cu2+ ions in aqueous solution and effluent from the Laxmi steel plant in Jodhpur, India. This type of composite represents a new class of hybrid ion exchangers with good ion exchange capacity, stability, reproducibility and selectivity for toxic metal ions found in effluent from the steel industry. The characterization of the resin was carried out by determining the ion-exchange capacity, elemental analysis, pH titration, Fourier transform infrared spectra and thermal analysis. The distribution coefficients (K(d)) of toxic metal ions were determined in a reference aqueous solution and the steel plant effluent at different pH values; the absorbency of different metal ions on the TSA resin was studied for up to 10 cycles. The adsorption of different metal ions on TSA resin follows the order: Co2+ > Cu2+ > Zn2+ > Fe2+ > Cd2+. The ion exchange capacity of TSA resin is 2.87%.

The role of metal ions in chemical evolution - Polymerization of alanine and glycine in a cation-exchanged clay environment

NASA Technical Reports Server (NTRS)

Lawless, J. G.; Levi, N.

1979-01-01

The effect of the exchangeable cation on the condensation of glycine and alanine was investigated using a series of homoionic bentonites. A cycling procedure of drying, warming and wetting was employed. Peptide bond formation was observed, and the effectiveness of metal ions to catalyze the condensation was Cu(2+) greater than Ni(2) approximately equals Zn(2+) greater than Na(+). Glycine showed 6% of the monomer incorporated into oligomers with the largest detected being the pentamer. Alanine showed less peptide bond formation (a maximum of 2%) and only the dimer was observed.

Electrically facilitated molecular transport. Analysis of the relative contributions of diffusion, migration, and electroosmosis to solute transport in an ion-exchange membrane.

PubMed

Bath, B D; White, H S; Scott, E R

2000-02-01

Electrically facilitated molecular transport in an ion-exchange membrane (Nafion, 1100 equiv wt) has been studied using a scanning electrochemical microscope. The transport rates of ferrocenylmethyltrimethylammonium (a cation), acetaminophen (a neutral molecule), and ascorbate (an anion) through approximately 120-micron-thick membranes were measured as a function of the iontophoretic current passed across the membrane (-1.0 to +1.0 A/cm2). Transport rates were analyzed by employing the Nernst-Planck equation, modified to account for electric field-driven convective transport. Excellent agreement between experimental and theoretical values of the molecular flux was obtained using a single fitting parameter for each molecule (electroosmotic drag coefficient). The electroosmotic velocity of the neutral molecule, acetaminophen, was shown to be a factor of approximately 500 larger than that of the cation ferrocenylmethyltrimethylammonium, a consequence of the electrostatic interaction of the cation with the negatively charged pore walls of the ion-exchange membrane. Electroosmotic transport of ascorbate occurred at a negligible rate due to repulsion of the anion by the cation-selective membrane. These results suggest that electroosmotic velocities of solute molecules are determined by specific chemical interactions of the permeant and membrane and may be very different from the average solution velocity. The efficiency of electroosmotic transport was also shown to be a function of the membrane thickness, in addition to membrane/solute interactions.

METHOD OF SEPARATING RARE EARTHS BY ION EXCHANGE

DOEpatents

Spedding, F.H.; Powell, J.E.

1960-10-18

A process is given for separating yttrium and rare earth values having atomic numbers of from 57 through 60 and 68 through 71 from an aqueous solution whose pH value can range from 1 to 9. All rare earths and yttrium are first adsorbed on a cation exchange resin, and they are then eluted with a solution of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) in the order of decreasing atomic number, yttrium behaving like element 61; the effluents are collected in fractions. The HEDTA is recovered by elution with ammonia solution and the resin is regenerated with sulfuric acid. Rare earths are precipitated from the various effluents with oxalic acid, and each supernatant is passed over cation exchange resin for adsorption of HEDTA and nonprecipitated rare earths: the oxalic acid is not retained by the resin.

Ion-exchange material and method of storing radioactive wastes

DOEpatents

Komarneni, S.; Roy, D.M.

1983-10-31

A new cation exchanger is a modified tobermorite containing aluminum isomorphously substituted for silicon and containing sodium or potassium. The exchanger is selective for lead, rubidium, cobalt, and cadmium and is selective for cesium over calcium or sodium. The tobermorites are compatible with cement and are useful for the long-term fixation and storage of radioactive nuclear wastes.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Microstructure and supercapacitive properties of buserite-type manganese oxide with a large basal spacing

NASA Astrophysics Data System (ADS)

Sun, Zhenjie; Shu, Dong; Chen, Hongyu; He, Chun; Tang, Shaoqing; Zhang, Jie

2012-10-01

A hydration-layered structure of buserite-type manganese oxide (Mg-buserite) was successfully synthesized by an ion exchange method. The as-prepared Mg-buserite possesses a large basal spacing of 10 Å, and contains Mg2+ ions and two sheets of water molecules in the interlayer region. The supercapacitive behaviors of Mg-buserite were systematically investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (CD) experiments and electrochemical impedance spectroscopy (EIS). The results showed that the specific capacitance of the Mg-buserite electrode sharply increased during the initial 500 cycles and reached a maximum of 164 F g-1 at approximately the 500th cycle at a scan rate of 1 mV s-1, and then it remained an almost constant value and decreased slightly upon prolonged cycling. After 22,000 cycles, the specific capacitance decreased by approximately 6% of the maximum specific capacitance. The superior capacitive behavior and excellent cycling stability of the as-prepared Mg-buserite are attributed to the large basal spacing, which can accommodate a larger amount of electrolyte cations and provide more favorable pathways for electrolyte cations intercalation and deintercalation. The experimental results demonstrate that Mg-buserite is a promising candidate as an electrode material for supercapacitors.

The reduction mechanism of chromite in the presence of a silica flux

NASA Astrophysics Data System (ADS)

Weber, P.; Eric, R. H.

1993-12-01

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe2+ ions and an inward diffusion of Mg2+ and Cr2+ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr3+ and Fe2+) in the spinel and the dissolved cations (Al3+ and Mg2+) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.

Deposition, Alteration, and Resuspension of Colorado River Delta Sediments, Lake Powell, Utah

NASA Astrophysics Data System (ADS)

Kramer, N. M.; Parnell, R.

2002-12-01

Current drought conditions in the southwest United States have resulted in lowering water levels in Lake Powell, Utah. Delta sediments forming at the Colorado River inflow for the past 39 years are becoming exposed and reworked as lake levels continue to fall to over 22 meters below full pool level. Fine sediments act as a sink for pollutants by adsorbing contaminants to their surfaces. Reworking these sediments may pose a risk to water quality in the lake. We examine whether burial and time have sufficiently altered fine sediments in the delta and affected materials adsorbed on their surfaces. Fifteen lake cores and six sediment traps were collected from the sediment delta forming at the Colorado River inflow in Lake Powell. This research characterizes fine sediment mineralogy, the composition of exchangeable materials, and organic matter content within delta sediments to determine the type and amount of alteration of these sediments with cycles of burial and resuspension. We hypothesize that as sediments are reworked, organic carbon is degraded and organic nitrogen is released forming ammonium in these reducing conditions. Sediment trap samples will be used to test this hypothesis. Trap samples will be compared to subsamples from sediment cores to determine the amount of alteration of fine sediments. All samples are analyzed for organic carbon, organic nitrogen, ammonium, cation exchange capacity, exchangeable cation composition, and clay mineralogy. Organic carbon and nitrogen are analyzed using a Leco CN analyzer. Ammonium is analyzed using a Lachet ion chromatograph. Clay mineralogy is characterized using a Siemens D500 powder X-ray diffractometer. Cation exchange capacity and exchangeable cations are measured using standard soil chemical techniques. Clay mineral analyses indicate significant spatial and temporal differences in fine sediment entering the Lake Powell delta which complicates the use of a simple deposition/alteration/resuspension model using a single starting material.

Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships

DOE PAGES

Hugar, Kristina M.; Kostalik, IV, Henry A.; Coates, Geoffrey W.

2015-06-11

Highly base-stable cationic moieties are a critical component of anion exchange membranes (AEMs) in alkaline fuel cells (AFCs); however, the commonly employed organic cations have limited alkaline stability. To address this problem, we synthesized and characterized the stability of a series of imidazolium cations in 1, 2, or 5 M KOH/CD 3OH at 80 °C, systematically evaluating the impact of substitution on chemical stability. The substituent identity at each position of the imidazolium ring has a dramatic effect on the overall cation stability. In conclusion, we report imidazolium cations that have the highest alkaline stabilities reported to date, >99% cationmore » remaining after 30 days in 5 M KOH/CD 3OH at 80 °C.« less

Unfolding of a model protein on ion exchange and mixed mode chromatography surfaces.

PubMed

Gospodarek, Adrian M; Hiser, Diana E; O'Connell, John P; Fernandez, Erik J

2014-08-15

Recent studies with proteins indicate that conformational changes and aggregation can occur during ion exchange chromatography (IEC). Such behavior is not usually expected, but could lead to decreased yield and product degradation from both IEC and multi mode chromatography (MMC) that has ligands of both hydrophobic and charged functionalities. In this study, we used hydrogen exchange mass spectrometry to investigate unfolding of the model protein BSA on IEC and MMC surfaces under different solution conditions at 25°C. Increased solvent exposure, indicating greater unfolding relative to that in solution, was found for protein adsorbed on cationic IEC and MMC surfaces in the pH range of 3.0 to 4.5, where BSA has decreased stability in solution. There was no effect of anionic surfaces at pH values in the range from 6.0 to 9.0. Differences of solvent exposure of whole molecules when adsorbed and in solution suggest that adsorbed BSA unfolds at lower pH values and may show aggregation, depending upon pH and the surface type. Measurements on digested peptides showed that classifications of stability can be made for various regions; these are generally retained as pH is changed. When salt was added to MMC systems, where electrostatic interactions would be minimized, less solvent exposure was seen, implying that it is the cationic moieties, rather than the hydrophobic ligands, which cause greater surface unfolding at low salt concentrations. These results suggest that proteins of lower stability may exhibit unfolding and aggregation during IEC and MMC separations, as they can with hydrophobic interaction chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

Alkalinity generation in snowmelt and rain runoff during short distance flow over rock

Treesearch

James L. Clayton

1998-01-01

High-elevation ecosystems in the western United States typically have patchy, discontinuous areas of surficial soils surrounded by large areas of rock outcrop, talus, and scree. Snowmelt and precipitation that percolate through soil increase in alkalinity, principally by increasing base cation concentration through cation exchange, and by decreasing acid anion...

CAX-ing a wide net: Cation/H(+) transporters in metal remediation and abiotic stress signalling

USDA-ARS?s Scientific Manuscript database

Cation/proton exchangers (CAXs) are a class of secondary energised ion transporter that are being implicated in an increasing range of cellular and physiological functions. CAXs are primarily Ca(2+) efflux transporters that mediate the sequestration of Ca(2+) from the cytosol, usually into the vacuo...

Dissolved Organic Carbon in Leachate after Application of Granular and Liquid N-P-K Fertilizers to a Sugarcane Soil.

PubMed

Pittaway, P A; Melland, A R; Antille, D L; Marchuk, S

2018-05-01

The progressive decline of soil organic matter (SOM) threatens the sustainability of arable cropping worldwide. Residue removal and burning, destruction of protected microsites, and the acceleration of microbial decomposition are key factors. Desorption of SOM by ammonia-based fertilizers from organomineral complexes in soil may also play a role. A urea- and molasses-based liquid fertilizer formulation and a urea-based granular formulation were applied at recommended and district practice rates, respectively, to soil leaching columns, with unfertilized columns used as controls. The chemistry of leachate collected from the columns, filled with two sandy soils differing in recent cropping history, was monitored over eight successive wet-dry drainage events. The pH, electrical conductivity, and concentration and species of N in leachate was compared with the concentration and aromaticity of dissolved organic C (DOC) to indicate if salt solutions derived from the two fertilizers extracted SOM from clay mineral sites. Cation exchange capacity and exchangeable cations in the soil were monitored at the start and end of the trial. Fertilizer application increased DOC in leachate up to 40 times above the control, but reduced aromaticity (specific ultraviolet light absorbance at 253.7 nm). Dissolved organic C was linearly proportional to leachate NH-N concentration. Exchangeable Ca and Mg in soil from fertilized columns at the end of both trials were significantly lower than in unfertilized soil, indicating that ammonium salt solutions derived from the fertilizers extracted cations and variably charged organic matter from soil mineral exchange sites. Desorption of organic matter and divalent cations from organomineral sites by ammonia-based fertilizers may be implicated in soil acidification. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Pharmaceuticals' sorptions relative to properties of thirteen different soils.

PubMed

Kodešová, Radka; Grabic, Roman; Kočárek, Martin; Klement, Aleš; Golovko, Oksana; Fér, Miroslav; Nikodem, Antonín; Jakšík, Ondřej

2015-04-01

Transport of human and veterinary pharmaceuticals in soils and consequent ground-water contamination are influenced by many factors, including compound sorption on soil particles. Here we evaluate the sorption isotherms for 7 pharmaceuticals on 13 soils, described by Freundlich equations, and assess the impact of soil properties on various pharmaceuticals' sorption on soils. Sorption of ionizable pharmaceuticals was, in many cases, highly affected by soil pH. The sorption coefficient of sulfamethoxazole was negatively correlated to soil pH, and thus positively related to hydrolytic acidity and exchangeable acidity. Sorption coefficients for clindamycin and clarithromycin were positively related to soil pH and thus negatively related to hydrolytic acidity and exchangeable acidity, and positively related to base cation saturation. The sorption coefficients for the remaining pharmaceuticals (trimethoprim, metoprolol, atenolol, and carbamazepine) were also positively correlated with the base cation saturation and cation exchange capacity. Positive correlations between sorption coefficients and clay content were found for clindamycin, clarithromycin, atenolol, and metoprolol. Positive correlations between sorption coefficients and organic carbon content were obtained for trimethoprim and carbamazepine. Pedotransfer rules for predicting sorption coefficients of various pharmaceuticals included hydrolytic acidity (sulfamethoxazole), organic carbon content (trimethoprimand carbamazepine), base cation saturation (atenolol and metoprolol), exchangeable acidity and clay content (clindamycin), and soil active pH and clay content (clarithromycin). Pedotransfer rules, predicting the Freundlich sorption coefficients, could be applied for prediction of pharmaceutical mobility in soils with similar soil properties. Predicted sorption coefficients together with pharmaceutical half-lives and other imputes (e.g., soil-hydraulic, geological, hydro-geological, climatic) may be used for assessing potential ground-water contamination. Copyright © 2014 Elsevier B.V. All rights reserved.

Isosteric heat of water adsorption and desorption in homoionic alkaline-earth montmorillonites

NASA Astrophysics Data System (ADS)

Belhocine, M.; Haouzi, A.; Bassou, G.; Phou, T.; Maurin, D.; Bantignies, J. L.; Henn, F.

2018-02-01

The aim of the present work is to study by means of thermodynamic measurements and Infrared spectroscopy, the effect of the interlayer cations on the adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e. the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The sorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at P/P∘ = 0.5 follows the cation sequence Ca ∼ Mg>Ba while the sorption isosteric heats follow a slightly different sequence, i.e. Ca > Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.

Insights into dynamic processes of cations in pyrochlores and other complex oxides

DOE PAGES

Uberuaga, Blas Pedro; Perriot, Romain

2015-08-26

Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

NASA Astrophysics Data System (ADS)

Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

2018-01-01

In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

Intracellular acidification-induced alkali metal cation/H+ exchange in human neutrophils

PubMed Central

1987-01-01

Pretreatment of isolated human neutrophils (resting pHi congruent to 7.25 at pHo 7.40) with 30 mM NH4Cl for 30 min leads to an intracellular acidification (pHi congruen to 6.60) when the NH4Cl prepulse is removed. Thereafter, in 140 mM Na+ medium, pHi recovers exponentially with time (initial rate, approximately 0.12 pH/min) to reach the normal resting pHi by approximately 20 min, a process that is accomplished mainly, if not exclusively, though an exchange of internal H+ for external Na+. This Na+/H+ countertransport is stimulated by external Na+ (Km congruent to 21 mM) and by external Li+ (Km congruent to 14 mM), though the maximal transport rate for Na+ is about twice that for Li+. Both Na+ and Li+ compete as substrates for the same translocation sites on the exchange carrier. Other alkali metal cations, such as K+, Rb+, or Cs+, do not promote pHi recovery, owing to an apparent lack of affinity for the carrier. The exchange system is unaffected by ouabain or furosemide, but can be competitively inhibited by the diuretic amiloride (Ki congruent to 8 microM). The influx of Na+ or Li+ is accompanied by an equivalent counter-reflux of H+, indicating a 1:1 stoichiometry for the exchange reaction, a finding consistent with the lack of voltage sensitivity (i.e., electroneutrality) of pHi recovery. These studies indicate that the predominant mechanism in human neutrophils for pHi regulation after intracellular acidification is an amiloride-sensitive alkali metal cation/H+ exchange that shares a number of important features with similar recovery processes in a variety of other mammalian cell types. PMID:3694176

Comparison between methods using copper, lanthanum, and colorimetry for the determination of the cation exchange capacity of plant cell walls.

PubMed

Wehr, J Bernhard; Blamey, F Pax C; Menzies, Neal W

2010-04-28

The determination of the cation exchange capacity (CEC) of plant cell walls is important for many physiological studies. We describe the determination of cell wall CEC by cation binding, using either copper (Cu) or lanthanum (La) ions, and by colorimetry. Both cations are strongly bound by cell walls, permitting fast and reproducible determinations of the CEC of small samples. However, the dye binding methods using two cationic dyes, Methylene Blue and Toluidine Blue, overestimated the CEC several-fold. Column and centrifugation methods are proposed for CEC determination by Cu or La binding; both provide similar results. The column method involves packing plant material (2-10 mg dry mass) in a chromatography column (10 mL) and percolating with 20 bed volumes of 1 mM La or Cu solution, followed by washing with deionized water. The centrifugation method uses a suspension of plant material (1-2 mL) that is centrifuged, and the pellet is mixed three times with 10 pellet volumes of 1 mM La or Cu solution followed by centrifugation and final washing with deionized water. In both methods the amount of La or Cu bound to the material was determined by spectroscopic methods.

Exploring Alkaline Stable Organic Cations for Polymer Hydroxide Exchange Membranes

DTIC Science & Technology

2015-04-29

1   1.1.2   Proton exchange membrane fuel cells ( PEMFCs ) ......................... 3   1.1.3   Alkaline fuel cells (AFCs...160   xi LIST OF FIGURES Figure 1.1:   Schematic diagram of a PEMFC ...according to the type of electrolyte they use. Nowadays, there are six major types of fuel cells: proton-exchange membrane fuel cells ( PEMFCs ), hydroxide

Ion exchange of H+, Na+, Mg2+, Ca2+, Mn2+, and Ba2+, on wood pulp

Treesearch

Alan W. Rudie; Alan Ball; Narendra Patel

2006-01-01

Ion exchange selectivity coefficients were measured for the partition of metals between solution and pulp fibers. The method accurately models the ion exchange isotherms for all cation pairs evaluated and is accurate up to approximately 0.05 molar concentrations. Selectivity coefficients were determined for calcium and magnesium with each other and with hydrogen....

Ion-exchange and iontophoresis-controlled delivery of apomorphine.

PubMed

Malinovskaja, Kristina; Laaksonen, Timo; Kontturi, Kyösti; Hirvonen, Jouni

2013-04-01

The objective of this study was to test a drug delivery system that combines iontophoresis and cation-exchange fibers as drug matrices for the controlled transdermal delivery of antiparkinsonian drug apomorphine. Positively charged apomorphine was bound to the ion-exchange groups of the cation-exchange fibers until it was released by mobile counter-ions in the external solution. The release of the drug was controlled by modifying either the fiber type or the ionic composition of the external solution. Due to high affinity of apomorphine toward the ion-exchanger, a clear reduction in the in vitro transdermal fluxes from the fibers was observed compared to the respective fluxes from apomorphine solutions. Changes in the ionic composition of the donor formulations affected both the release and iontophoretic flux of the drug. Upon the application of higher co-ion concentrations or co-ions of higher valence in the donor formulation, the release from the fibers was enhanced, but the iontophoretic steady-state flux was decreased. Overall, the present study has demonstrated a promising approach using ion-exchange fibers for controlling the release and iontophoretic transdermal delivery of apomorphine. Copyright © 2012 Elsevier B.V. All rights reserved.

Microbial desalination cell with sulfonated sodium poly(ether ether ketone) as cation exchange membranes for enhancing power generation and salt reduction.

PubMed

Moruno, Francisco Lopez; Rubio, Juan E; Atanassov, Plamen; Cerrato, José M; Arges, Christopher G; Santoro, Carlo

2018-06-01

Microbial desalination cell (MDC) is a bioelectrochemical system capable of oxidizing organics, generating electricity, while reducing the salinity content of brine streams. As it is designed, anion and cation exchange membranes play an important role on the selective removal of ions from the desalination chamber. In this work, sulfonated sodium (Na + ) poly(ether ether ketone) (SPEEK) cation exchange membranes (CEM) were tested in combination with quaternary ammonium chloride poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membrane (AEM). Non-patterned and patterned (varying topographical features) CEMs were investigated and assessed in this work. The results were contrasted against a commercially available CEM. This work used real seawater from the Pacific Ocean in the desalination chamber. The results displayed a high desalination rate and power generation for all the membranes, with a maximum of 78.6±2.0% in salinity reduction and 235±7mWm -2 in power generation for the MDCs with the SPEEK CEM. Desalination rate and power generation achieved are higher with synthesized SPEEK membranes when compared with an available commercial CEM. An optimized combination of these types of membranes substantially improves the performances of MDC, making the system more suitable for real applications. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

PROCESS OF PRODUCING Cm$sup 244$ AND Cm$sup 24$$sup 5$

DOEpatents

Manning, W.M.; Studier, M.H.; Diamond, H.; Fields, P.R.

1958-11-01

A process is presented for producing Cm and Cm/sup 245/. The first step of the process consists in subjecting Pu/sup 2339/ to a high neutron flux and subsequently dissolving the irradiated material in HCl. The plutonium is then oxidized to at least the tetravalent state and the solution is contacted with an anion exchange resin, causing the plutonium values to be absorbed while the fission products and transplutonium elements remain in the effluent solution. The effluent solution is then contacted with a cation exchange resin causing the transplutonium, values to be absorbed while the fission products remain in solution. The cation exchange resin is then contacted with an aqueous citrate solution and tbe transplutonium elements are thereby differentially eluted in order of decreasing atomic weight, allowing collection of the desired fractions.

Separation of Pb, Bi and Po by cation exchange resin

DOE PAGES

Kmak, Kelly N.; Despotopulos, John D.; Shaughnessy, Dawn A.

2017-09-27

In this paper, a separation of 209Po, 207Bi and 212Pb using AG 50Wx8 and AG MP 50 cation exchange resins in an HCl medium was developed. A procedure in which Po(IV) elutes first in 0.2 M HCl, followed by Bi(III) in 0.4 M HCl and finally Pb(II) in 2 M HCl was established. The separation using AG 50Wx8 provides a much better elution profile than that of AG MP 50 with no overlap between the elution bands. Finally, this separation has the potential to be used as an isotope generator for producing 210Po from 210Pb.

CATIONIC EXCHANGE PROCESS FOR THE SEPARATION OF RARE EARTHS

DOEpatents

Choppin, G.R.; Thompson, S.G.; Harvey, B.G.

1960-02-16

A process for separating mixtures of elements in the lanthanum and actinium series of the periodic table is described. The mixture of elements is dissolved in 0.05 M HCI, wherein the elements exist as tripositive ions. The resulting solution is then transferred to a column of cationic exchange resin and the column eluted with 0.1 to 0.6 M aqueous ammonium alpha hydroxy isobutyrate solution of pH 3.8 to 5.0. The use of ammonium alpha hydroxy isobutyrate as an eluting agent results in sharper and more rapid separations than previously obtainable with eluants such as citric, tartaric, glycolic, and lactic acids.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Geochemical modulation of bioavailability and toxicity of nitroaromatic compounds to aquatic plants.

PubMed

Roberts, Michael G; Rugh, Clayton L; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2007-03-01

Nitroaromatic compounds (NACs) are prominent soil and sediment contaminants that are strongly adsorbed by smectites at extents that depend on hydration properties of the exchangeable cation. Potassium smectites adsorb nitroaromatics much more strongly than calcium smectites, so that adjustment of K+ versus Ca2+ occupation on cation exchange sites in smectites can be used to modulate the retention and release of nitroaromatics. We suggest that this modulation can be used to advantageously manage the bioavailability and toxicity of NACs during bioremedation. We have measured the toxicity of 2,4-dinitrotoluene (2,4-DNT) to duckweed grown in smectite suspensions and utilized Ca2+/K+ exchange to retain or release 2,4-DNT. Retention by potassium smectite reduced bioavailability and hence toxicity to duckweed. Addition of Ca2+ to replace K+ by ion exchange released adsorbed 2,4-DNT, which is toxic to duckweed. So smectites can be used to sequester or release 2,4-DNT predictably and provide means to control bioavailability and environmental toxicity.

Synthesis of Silver Embedded Poly(o-Anisidine) Molybdophosphate Nano Hybrid Cation-Exchanger Applicable for Membrane Electrode

PubMed Central

Khan, Anish; Khan, Aftab Aslam Parwaz; Asiri, Abdullah M.; Rub, Malik Abdul

2014-01-01

Poly(o-anisidine) molybdophosphate was expediently obtained by sol-gel mixing of Poly(o-anisidine) into the inorganic matrices of molybdophosphate, which was allowed to react with silver nitrate to the formation of poly(o-anisidine) molybdophosphate embedded silver nano composite. The composite was characterized by Fourier Transform Infrared Spectroscopy, X-ray powder diffraction, UV-Vis Spectrophotometry, Fluorescence Spectroscopy, Scanning Electron Microscopy/Energy-dispersive X-ray Spectroscopy and Thermogravimertic Analysis. Ion exchange capacity and distribution studies were carried out to understand the ion-exchange capabilities of the nano composite. On the basis of highest distribution studies, this nano composite cation exchanger was used as preparation of heavy metal ion selective membrane. Membrane was characterized for its performance as porosity and swelling later on was used for the preparation of membrane electrode for Hg(II), having better linear range, wide working pH range (2–4.5) with fast response in the real environment. PMID:24805257

Extraction and derivatization of chemical weapons convention relevant aminoalcohols on magnetic cation-exchange resins.

PubMed

Singh, Varoon; Garg, Prabhat; Chinthakindi, Sridhar; Tak, Vijay; Dubey, Devendra Kumar

2014-02-14

Analysis and identification of nitrogen containing aminoalcohols is an integral part of the verification analysis of chemical weapons convention (CWC). This study was aimed to develop extraction and derivatization of aminoalcohols of CWC relevance by using magnetic dispersive solid-phase extraction (MDSPE) in combination with on-resin derivatization (ORD). For this purpose, sulfonated magnetic cation-exchange resins (SMRs) were prepared using magnetite nanoparticles as core, styrene and divinylbenzene as polymer coat and sulfonic acid as acidic cation exchanger. SMRs were successfully employed as extractant for targeted basic analytes. Adsorbed analytes were derivatized with hexamethyldisilazane (HMDS) on the surface of extractant. Derivatized (silylated) compounds were analyzed by GC-MS in SIM and full scan mode. The linearity of the method ranged from 5 to 200ngmL(-1). The LOD and LOQ ranged from 2 to 6ngmL(-1) and 5 to 19ngmL(-1) respectively. The relative standard deviation for intra-day repeatability and inter-day intermediate precision ranged from 5.1% to 6.6% and 0.2% to 7.6% respectively. Recoveries of analytes from spiked water samples from different sources varied from 28.4% to 89.3%. Copyright © 2014 Elsevier B.V. All rights reserved.

Method for ultra-trace cesium isotope ratio measurements from environmental samples using thermal ionization mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snow, Mathew S.; Snyder, Darin C.; Mann, Nick R.

2015-05-01

135Cs/ 137Cs isotope ratios can provide the age, origin and history of environmental Cs contamination. Relatively high precision 135Cs/ 137Cs isotope ratio measurements from samples containing femtogram quantities of 137Cs are needed to accurately track contamination resuspension and redistribution following environmental 137Cs releases; however, mass spectrometric analyses of environmental samples are limited by the large quantities of ionization inhibitors and isobaric interferences which are present at relatively high concentrations in the environment. We report a new approach for Cs purification from environmental samples. An initial ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) column provides a robust method for extracting Cs under a wide varietymore » of sample matrices and mass loads. Cation exchange separations using a second AMP-PAN column result in more than two orders of magnitude greater Cs/Rb separation factors than commercially available strong cation exchangers. Coupling an AMP-PAN cation exchanging step to a microcation column (AG50W resin) enables consistent 2-4% (2σ) measurement errors for samples containing 3-6,000 fg 137Cs, representing the highest precision 135Cs/ 137Cs ratio measurements currently reported for soil samples at the femtogram level.« less

Capillary trap column with strong cation-exchange monolith for automated shotgun proteome analysis.

PubMed

Wang, Fangjun; Dong, Jing; Jiang, Xiaogang; Ye, Mingliang; Zou, Hanfa

2007-09-01

A 150 microm internal diameter capillary monolithic column with a strong cation-exchange stationary phase was prepared by direct in situ polymerization of ethylene glycol methacrylate phosphate and bisacrylamide in a trinary porogenic solvent consisting dimethylsulfoxide, dodecanol, and N,N'-dimethylformamide. This phosphate monolithic column exhibits higher dynamic binding capacity, faster kinetic adsorption of peptides, and more than 10 times higher permeability than the column packed with commercially available strong cation-exchange particles. It was applied as a trap column in a nanoflow liquid chromatography-tandem mass spectrometry system for automated sample injection and online multidimensional separation. It was observed that the sample could be loaded at a flow rate as high as 40 microL/min with a back pressure of approximately 1300 psi and without compromising the separation efficiency. Because of its good orthogonality to the reversed phase separation mechanism, the phosphate monolithic trap column was coupled with a reversed-phase column for online multidimensional separation of 19 microg of the tryptic digest of yeast proteins. A total of 1522 distinct proteins were identified from 5608 unique peptides (total of 54,780 peptides) at the false positive rate only 0.46%.

Uncertainties of Gaseous Oxidized Mercury Measurements Using KCl-Coated Denuders, Cation-Exchange Membranes, and Nylon Membranes: Humidity Influences.

PubMed

Huang, Jiaoyan; Gustin, Mae Sexauer

2015-05-19

Quantifying the concentration of gaseous oxidized mercury (GOM) and identifying the chemical compounds in the atmosphere are important for developing accurate local, regional, and global biogeochemical cycles. The major hypothesis driving this work was that relative humidity affects collection of GOM on KCl-coated denuders and nylon membranes, both currently being applied to measure GOM. Using a laboratory manifold system and ambient air, GOM capture efficiency on 3 different collection surfaces, including KCl-coated denuders, nylon membranes, and cation-exchange membranes, was investigated at relative humidity ranging from 25 to 75%. Recovery of permeated HgBr2 on KCl-coated denuders declined by 4-60% during spikes of relative humidity (25 to 75%). When spikes were turned off GOM recoveries returned to 60 ± 19% of permeated levels. In some cases, KCl-coated denuders were gradually passivated over time after additional humidity was applied. In this study, GOM recovery on nylon membranes decreased with high humidity and ozone concentrations. However, additional humidity enhanced GOM recovery on cation-exchange membranes. In addition, reduction and oxidation of elemental mercury during experiments was observed. The findings in this study can help to explain field observations in previous studies.

Deterioration of soil fertility by land use changes in South Sumatra, Indonesia: from 1970 to 1990

NASA Astrophysics Data System (ADS)

Lumbanraja, Jamalam; Syam, Tamaluddin; Nishide, Hiroyo; Kabul Mahi, Ali; Utomo, Muhajir; Sarno; Kimura, Makoto

1998-10-01

We monitored the land use changes in a hilly area of West Lampung, South Sumatra, Indonesia, from 1970 to 1990. The main data sources were the land use maps produced in 1970, 1978, 1984 and 1990 covering the area of 27 km×27 km. Transmigration and the resultant effect of increased population were the major driving forces in land use changes. Fifty-seven per cent of the study area was covered with primary forests in 1970, but only 13% in 1990. Areas under plantations, which were absent in 1970, increased to 60% in 1990. In addition, the change from monoculture plantations (mostly coffee plantation) to mixed plantations was noticeable from 1984 to 1990. Total upland areas including upland areas under shifting cultivation and upland fields with crops and vegetables decreased from 21% in 1970 to 0·1% in 1990. Soil chemical properties (total organic C, total N, available P, total P, exchangeable cations, cation exchangeable capacity (CEC), etc.) were analysed for lands under different land use forms after deforestation in the study area. Soil samples (surface layers, 0-20 cm, and subsurface layers, 20-40 cm) were collected from three different locations, each comprised of four different land use systems: i.e. primary forests, secondary forests, coffee plantations and cultivated lands. The contents of total organic C, total N, available P, total P, exchangeable cations and CEC decreased significantly with land use change from primary forests to the other land use forms. Cultivated lands exhibited the lowest values. Although less remarkable than in the surface layers, the amounts of total organic C, total N, total P, exchangeable cations and CEC were also decreased by forest clearing in the subsurface layers.Based on the land use changes from 1978 in the study area and the deterioration of soil chemical properties by forest clearing, total decreases in the amounts of nutrients in the surface and subsurface layers were estimated. The land use changes were estimated to have decreased the total amounts of total organic C, total N, available P, total P, exchangeable cations and CEC by 2-9% in 1984 and by 2-15% in 1990 in the surface layers, and by 1-6%% in 1984 and by 2-9% in 1990 in the subsurface layers from the levels in 1978, respectively.

Synergistic effects on enantioselectivity of zwitterionic chiral stationary phases for separations of chiral acids, bases, and amino acids by HPLC.

PubMed

Hoffmann, Christian V; Pell, Reinhard; Lämmerhofer, Michael; Lindner, Wolfgang

2008-11-15

In an attempt to overcome the limited applicability scope of earlier proposed Cinchona alkaloid-based chiral weak anion exchangers (WAX) and recently reported aminosulfonic acid-based chiral strong cation exchangers (SCX), which are conceptionally restricted to oppositely charged solutes, their individual chiral selector (SO) subunits have been fused in a combinatorial synthesis approach into single, now zwitterionic, chiral SO motifs. The corresponding zwitterionic ion-exchange-type chiral stationary phases (CSPs) in fact combined the applicability spectra of the parent chiral ion exchangers allowing for enantioseparations of chiral acids and amine-type solutes in liquid chromatography using polar organic mode with largely rivaling separation factors as compared to the parent WAX and SCX CSPs. Furthermore, the application spectrum could be remarkably expanded to various zwitterionic analytes such as alpha- and beta-amino acids and peptides. A set of structurally related yet different CSPs consisting of either a quinine or quinidine alkaloid moiety as anion-exchange subunit and various chiral or achiral amino acids as cation-exchange subunits enabled us to derive structure-enantioselectivity relationships, which clearly provided strong unequivocal evidence for synergistic effects of the two oppositely charged ion-exchange subunits being involved in molecular recognition of zwitterionic analytes by zwitterionic SOs driven by double ionic coordination.

The effect of Sinabung volcanic ash and rock phosphate nanoparticle on CEC (cation exchange capacity) base saturation exchange (K, Na, Ca, Mg) and base saturation at Andisol soils Ciater, West Java

NASA Astrophysics Data System (ADS)

Yuniarti, Anni; Arifin, Mahfud; Sofyan, Emma Trinurasi; Natalie, Betty; Sudirja, Rija; Dahliani, Dewi

2018-02-01

Andisol, soil orders which covers an upland area dominantly. The aim of this research is to know the effect between the ameliorant of Sinabung volcanic ashes with the ameliorant of rock phosphatenanoparticle towards CEC and base saturation exchange (K, Na, Ca, Mg) and the base saturation on Ciater's Andisols, West Java. A randomized complete block design (RCBD) factorial with two factors was used in this research. The first factor is the volcanic ash and the second factor is rock phosphate which consists of four levels each amount of 0%, 2.5%, 5%, 7.5% with three replications. The result showed that there was no interaction between volcanic ash and rock phosphate nanoparticle formed in first month and fourth month towards the improvement of CEC and saturation base exchange rate unless magnesium cation exchange increased in fourth month. There was independent effect of volcanic ash formed nanoparticles towards base saturation exchange increased for 5% dose. There was independent effect of rock phosphate formed nanoparticles towards base saturation exchange and increased for 5% dose. The dose combination of volcanic ashes 7.5% with phosphate rock, 5% increased the base saturation in the first month incubation.

Long-term effects of commercial sawlog harvest on soil cation concentrations

Treesearch

Jennifer D. Knoepp; Wayne T. Swank

1997-01-01

There is increasing concern about the effects of nutrient removal associated with various forest harvesting practices on long-term site productivity. The authors measured exchangeable soil cation concentration responses to a commercial clearcut sawlog harvest in mixed hardwoods on a 59-ha watershed in the Southern Appalachians. Soils were sampled 17 months prior to and...

Determination of labile copper, cobalt, and chromium in textile mill wastewater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crain, J.S.; Essling, A.M.; Kiely, J.T.

1997-01-01

Copper, chromium, and cobalt species present in filtered wastewater effluent were separated by cation exchange and reverse phase chromatography. Three sample fractions were obtained: one containing metal cations (i.e., trivalent Cr, divalent Cu, and divalent Co), one containing organic species (including metallized dyes), and one containing other unretained species. The metal content of each fraction was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The sum of the corrected data was compared to the metal content of a filtered effluent aliquot digested totally with fuming sulfuric acid. Other aliquots of the filtered effluent were spiked with the metals ofmore » interest and digested to confirm chemical yield and accuracy. Method detection limits were consistently below 20 {mu}g L{sup -1} for Cu, 30 {mu}g L{sup -1} for Co, and 10 {mu}g L{sup -1} for Cr. Spike recoveries for undifferentiated Cu and Cr were statistically indistinguishable from unity; although Co spike recoveries were slightly low ({approximately}95%), its chemical yield was 98%. Copper retention on the sodium sulfonate cation exchange resin was closely correlated with the [EDTA]/[Cu] ratio, suggesting that metals retained upon the cation exchange column were assignable to labile metal species; however, mass balances for all three elements, though reasonable ({approximately}90%), were significantly different from unity. Mechanical factors may have contributed to the material loss, but other data suggest that some metal species reacted irreversibly with the reverse phase column. 3 refs., 2 figs., 4 tabs.« less

EVALUATING ION EXCHANGE FOR REMOVING RADIUM FROM GROUNDWATER

EPA Science Inventory

This article, the second in a series, focuses on the results of bench- and pilot-scale studies of ion exchange processes for radium removal from groundwater in Lemont, Ill. Batch and column studies indicated a very high resin selectivity for radium compared with common cations. E...

Preparation and Characterization of an Alkaline Anion Exchange Membrane from Chlorinated Poly(propylene) Aminated with Branched Poly(ethyleneimine)

DTIC Science & Technology

2013-01-01

exchange resins and as membranes for water purification [1], Li–air batteries, and in polymer exchange membrane ( PEM ) fuel cells [2]. PEM Fuel cells show...SUBJECT TERMS Anion exchange membrane, Fuel Cell , Poly(ethyleneimine), Quaternary ammonium caton, Hydroxide Ashley M. Maes, Tara P. Pandey, Melissa...membrane Fuel cell Poly(ethyleneimine) Quaternary ammonium cation Hydroxide a b s t r a c t A new randomly crosslinked polymer is investigated

Electrogenic Na+/Ca2+ Exchange

PubMed Central

Danaceau, Jonathan P.; Lucero, Mary T.

2000-01-01

Olfactory receptor neurons (ORNs) from the squid, Lolliguncula brevis, respond to the odors l-glutamate or dopamine with increases in internal Ca2+ concentrations ([Ca2+]i). To directly asses the effects of increasing [Ca2+]i in perforated-patched squid ORNs, we applied 10 mM caffeine to release Ca2+ from internal stores. We observed an inward current response to caffeine. Monovalent cation replacement of Na+ from the external bath solution completely and selectively inhibited the caffeine-induced response, and ruled out the possibility of a Ca2+-dependent nonselective cation current. The strict dependence on internal Ca2+ and external Na+ indicated that the inward current was due to an electrogenic Na+/Ca2+ exchanger. Block of the caffeine-induced current by an inhibitor of Na+/Ca2+ exchange (50–100 μM 2′,4′-dichlorobenzamil) and reversibility of the exchanger current, further confirmed its presence. We tested whether Na+/Ca2+ exchange contributed to odor responses by applying the aquatic odor l-glutamate in the presence and absence of 2′,4′-dichlorobenzamil. We found that electrogenic Na+/Ca2+ exchange was responsible for ∼26% of the total current associated with glutamate-induced odor responses. Although Na+/Ca2+ exchangers are known to be present in ORNs from numerous species, this is the first work to demonstrate amplifying contributions of the exchanger current to odor transduction. PMID:10828249

THERMODYNAMICS OF ION-EXCHANGED NATURAL CLINOPTILOLITE

EPA Science Inventory

Natural clinoptilolite from Castle Creek, Idaho, and its cation-exchanged variants (Na-Cpt, NaK-Cpt, K-Cpt, and Ca-Cpt) were studied by high-temperature calorimetry. The hydration enthalpy for all clinoptilolites is about -30 kJ/mol H2O (liquid water reference state) at 25 C. T...

A new configuration of membrane stack for retrieval of nickel absorbed in resins*

PubMed Central

Chen, Xue-fen; Wu, Zu-cheng

2005-01-01

A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchange resins without additive chemicals. By simply assembling cation exchange resins and anion exchange resins separated by homogeneous membranes, we found that the system will always be acidic in the concentrate compartment so that ion exchange resins could be in-situ regenerated without hydroxide precipitation. Such a realizable design will be really suitable for wastewater purification. PMID:15909341

Morphological and physical behavior of styrenic, phosphonium-containing ionomers

NASA Astrophysics Data System (ADS)

Beyer, Rick; Stokes, Kristoffer

2010-03-01

Despite many years of effort, a clear understanding of the factors controlling morphology in Nafion and other ionomers has not been achieved. The increasing need for fuel cell technology continues to drive efforts to develop materials having better performance characteristics even though fundamental structure-property relationships remain unclarified. Alkaline fuel cells (AFCs) present several benefits over proton exchange membrane (PEM) fuel cells, including cost of manufacture (less expensive catalysts) and a significantly shorter path to commercialization. Here we present the most recent findings from our efforts to examine structure-morphology-property relationships for a series of model cationic ionomers. A series of statistical copolymers of styrene and p-vinylbenzyl-trimethyl-phosphonium chloride have been prepared via RAFT polymerization, allowing us to investigate the effect of ion content on physical behavior. Chemical, physical, and morphological characterization has been undertaken using NMR, TGA, DSC, SAXS, and TEM.

Thermodynamics of feldspathoid solutions

NASA Astrophysics Data System (ADS)

Sack, Richard O.; Ghiorso, Mark S.

We have developed models for the thermody-namic properties of nephelines, kalsilites, and leucites in the simple system NaAlSiO4-KAlSiO4-Ca0.5AlSiO4-SiO2-H2O that are consistent with all known constraints on subsolidus equilibria and thermodynamic properties, and have integrated them into the existing MELTS software package. The model for nepheline is formulated for the simplifying assumptions that (1) a molecular mixing-type approximation describes changes in the configurational entropy associated with the coupled exchange substitutions □Si?NaAl and □Ca? Na2 and that (2) Na+ and K+ display long-range non-convergent ordering between a large cation and the three small cation sites in the Na4Al4Si4O16 formula unit. Notable features of the model include the prediction that the mineral tetrakalsilite (``panunzite'', sensu stricto) results from anti-ordering of Na and K between the large cation and the three small cation sites in the nepheline structure at high temperatures, an average dT/dP slope of about 55°/kbar for the reaction over the temperature and pressure ranges 800-1050 °C and 500-5000 bars, roughly symmetric (i.e. quadratic) solution behavior of the K-Na substitution along joins between fully ordered components in nepheline, and large positive Gibbs energies for the nepheline reciprocal reactions and and for the leucite reciprocal reaction

Effect of Monovalent Ion Parameters on Molecular Dynamics Simulations of G-Quadruplexes.

PubMed

Havrila, Marek; Stadlbauer, Petr; Islam, Barira; Otyepka, Michal; Šponer, Jiří

2017-08-08

G-quadruplexes (GQs) are key noncanonical DNA and RNA architectures stabilized by desolvated monovalent cations present in their central channels. We analyze extended atomistic molecular dynamics simulations (∼580 μs in total) of GQs with 11 monovalent cation parametrizations, assessing GQ overall structural stability, dynamics of internal cations, and distortions of the G-tetrad geometries. Majority of simulations were executed with the SPC/E water model; however, test simulations with TIP3P and OPC water models are also reported. The identity and parametrization of ions strongly affect behavior of a tetramolecular d[GGG] 4 GQ, which is unstable with several ion parametrizations. The remaining studied RNA and DNA GQs are structurally stable, though the G-tetrad geometries are always deformed by bifurcated H-bonding in a parametrization-specific manner. Thus, basic 10-μs-scale simulations of fully folded GQs can be safely done with a number of cation parametrizations. However, there are parametrization-specific differences and basic force-field errors affecting the quantitative description of ion-tetrad interactions, which may significantly affect studies of the ion-binding processes and description of the GQ folding landscape. Our d[GGG] 4 simulations indirectly suggest that such studies will also be sensitive to the water models. During exchanges with bulk water, the Na + ions move inside the GQs in a concerted manner, while larger relocations of the K + ions are typically separated. We suggest that the Joung-Cheatham SPC/E K + parameters represent a safe choice in simulation studies of GQs, though variation of ion parameters can be used for specific simulation goals.

CEC-normalized clay-water sorption isotherm

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.

2011-11-01

A normalized clay-water isotherm model based on BET theory and describing the sorption and desorption of the bound water in clays, sand-clay mixtures, and shales is presented. Clay-water sorption isotherms (sorption and desorption) of clayey materials are normalized by their cation exchange capacity (CEC) accounting for a correction factor depending on the type of counterion sorbed on the mineral surface in the so-called Stern layer. With such normalizations, all the data collapse into two master curves, one for sorption and one for desorption, independent of the clay mineralogy, crystallographic considerations, and bound cation type; therefore, neglecting the true heterogeneity of water sorption/desorption in smectite. The two master curves show the general hysteretic behavior of the capillary pressure curve at low relative humidity (below 70%). The model is validated against several data sets obtained from the literature comprising a broad range of clay types and clay mineralogies. The CEC values, derived by inverting the sorption/adsorption curves using a Markov chain Monte Carlo approach, are consistent with the CEC associated with the clay mineralogy.

Atomic-scale models of early-stage alkali depletion and SiO2-rich gel formation in bioactive glasses.

PubMed

Tilocca, Antonio

2015-01-28

Molecular dynamics simulations of Na(+)/H(+)-exchanged 45S5 Bioglass® models reveal that a large fraction of the hydroxyl groups introduced into the proton-exchanged, hydrated glass structure do not initially form covalent bonds with Si and P network formers but remain free and stabilised by the modifier metal cations, whereas substantial Si-OH and P-OH bonding is observed only at higher Na(+)/H(+) exchange levels. The strong affinity between free OH groups and modifier cations in the highly fragmented 45S5 glass structure appears to represent the main driving force for this effect. This suggests an alternative direct route for the formation of a repolymerised silica-rich gel in the early stages of the bioactive mechanism, not considered before, which does not require sequential repeated breakings of Si-O-Si bonds and silanol condensations.

Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

2015-11-14

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

PubMed

Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

2014-09-01

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process.

PubMed

Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V

2011-12-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. © The Author(s) 2011. Published by Oxford University Press.

Organic molecules as sorbing tracers for the assessment of surface areas in consolidated aquifer systems

NASA Astrophysics Data System (ADS)

Schaffer, Mario; Warner, Wiebke; Kutzner, Susann; Börnick, Hilmar; Worch, Eckhard; Licha, Tobias

2017-03-01

Based on the assumption that the specific surface area to volume ratio Asurf/V of consolidated rock materials is proportional to the surface area available for sorption, several inorganic cations were recently proposed as sorbing (cation exchanging) tracers for estimating these ratios in aquifers (e.g., for deriving the efficient heat exchange area of geothermal reservoirs). The main disadvantages of inorganic ions, however, are the limited number of suitable ions, their potential geogenic background, and their challenging online detection at trace concentrations. In this work, the spectrum of chemical substances used as sorbing tracers expands by considering fluorescent organic compounds that are cationic. They have the advantage of being highly water soluble and easy to measure online at very low concentrations. Results from systematic lab column experiments with seven selected organic cations under various conditions (different salinities and temperatures) are presented, emphasizing the potential of organic molecules as alternative sorbing tracers especially in consolidated aquifer systems. This work is a first stepping stone in identifying suitable molecular structures that can be selected or even individually adapted to the requirements of the tracer tests and prevailing aquifer conditions.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process

PubMed Central

Reshetnikov, Roman V.; Sponer, Jiri; Rassokhina, Olga I.; Kopylov, Alexei M.; Tsvetkov, Philipp O.; Makarov, Alexander A.; Golovin, Andrey V.

2011-01-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. PMID:21893589

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

NASA Astrophysics Data System (ADS)

Chavan, Vivek; Agarwal, Chhavi; Shinde, Rakesh N.

2018-06-01

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

XPS characterization of silver exchanged ETS-10 and mordenite molecular sieves.

PubMed

Anson, A; Maham, Y; Lin, C C H; Kuznicki, T M; Kuznicki, S M

2009-05-01

Silver exchanged molecular sieves ETS-10 (Ag-ETS-10) and mordenite (Ag-mordenite) were dehydrated under vacuum at temperatures between 100 degrees C-350 degrees C. Changes in the state of the silver were studied using X-ray photoelectron spectroscopy (XPS). Silver cations in titanosilicate Ag-ETS-10 are fully reduced to Ag(0) at temperatures as low as 150 degrees C. The characteristic features of the XPS spectrum of silver in this Ag-ETS-10 species correspond to only metallic silver. The signal for metallic silver is not observed in the XPS spectrum of aluminosilicate Ag-mordenite, indicating that silver cations are not reduced, even after heating to 350 degrees C.

ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

DOEpatents

Kennedy, J.

1959-04-14

An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.

Strong Cation Exchange Chromatography in Analysis of Posttranslational Modifications: Innovations and Perspectives

PubMed Central

Edelmann, Mariola J.

2011-01-01

Strong cation exchange (SCX) chromatography has been utilized as an excellent separation technique that can be combined with reversed-phase (RP) chromatography, which is frequently used in peptide mass spectrometry. Although SCX is valuable as the second component of such two-dimensional separation methods, its application goes far beyond efficient fractionation of complex peptide mixtures. Here I describe how SCX facilitates mapping of the protein posttranslational modifications (PTMs), specifically phosphorylation and N-terminal acetylation. The SCX chromatography has been mainly used for enrichment of these two PTMs, but it might also be beneficial for high-throughput analysis of other modifications that alter the net charge of a peptide. PMID:22174558

Hafnium radioisotope recovery from irradiated tantalum

DOEpatents

Taylor, Wayne A.; Jamriska, David J.

2001-01-01

Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

Ion Exchange Polymeric Coatings for Selective Capacitive Deionization

NASA Astrophysics Data System (ADS)

Jain, Amit; Kim, Jun; Li, Qilin; Verduzco, Rafael

Capacitive deionization (CDI) is an energy-efficient technology for adsorbing and removing scalants and foulants from water by utilizing electric potential between porous carbon electrodes. Currently, industrial application of CDI is limited to low salinity waters due to the limited absorption capacities of carbon electrodes. However, CDI can potentially be used as a low-cost approach to selectively remove divalent ions from high salinity water. Divalent ions such as sulfonates and carbonates cause scaling and thus performance deterioration of membrane-based desalination systems. In this work, we investigated ion-exchange polymer coatings for use in a membrane capacitive deionization (MCDI) process for selective removal of divalent ions. Poly-Vinyl Alcohol (PVA) base polymer was crosslinked and charged using sulfo-succinic acid (SSA) to give a cation exchange layer. 50 um thick standalone polymer films had a permeability of 4.25*10-7 cm2/s for 10mM NaCl feed. Experiments on electrodes with as low as 10 υm thick coating of cation exchange polymer are under progress and will be evaluated on the basis of their selective salt removal efficiency and charge efficiency, and in future we will extend this work to sulfonated block copolymers and anion exchange polymers.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Structural behavior of ZnCr 2S 4 spinel under pressure

DOE PAGES

Efthimiopoulos, I.; Lochbiler, T.; Tsurkan, V.; ...

2016-12-15

Here, the series of Cr-chalcogenide spinels ACr 2X 4 (A = Zn, Cd, Hg; X = S, Se) exhibits a rich phase diagram upon compression, as revealed by our recent investigations. There exist, however, some open questions regarding the role of cations in the observed structural transitions. In order to address these queries, we have performed X-ray diffraction and Raman spectroscopic studies on the ZnCr 2S 4 spinel up to 42 GPa, chosen mainly due to the similarity of the Zn 2+ and Cr 3+ cationic radii. Two reversible structural transitions were identified at 22 and 33 GPa, into a I4 1/ amd and an orthorhombic phase, respectively. Close comparison with the behavior of relevant Cr-spinels revealed that the structural transitions are mainly governed by the competition of the magnetic exchange interactions present in these systems, and not by steric effects. In addition, careful inspection of the starting Fdmore » $$\\bar{3}$$m phase revealed a previously unnoticed isostructural transition. The latter is intimately related to changes in the electronic properties of these systems, as evidenced by our Raman studies. Our results provide insights for tuning the physical and chemical properties of these materials, even under moderate compression, as well as promoting the understanding of similar pressure-induced effects in relevant systems.« less

Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan

2016-04-06

Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na +, K +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Pb 2+ equilibrated at 43% relative humidity (RH) and mixed with 2H 2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H 2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with themore » 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H 2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H 2O molecules around their dipoles, reorientation of the 2H 2O molecules, and exchange of the 2H 2O molecules between interlayer sites coordinated to and not coordinated to the cations.« less

Magnetic and hyperthermia properties of CoxFe3-xO4 nanoparticles synthesized via cation exchange

NASA Astrophysics Data System (ADS)

Mohapatra, Jeotikanta; Xing, Meiying; Liu, J. Ping

2018-05-01

We demonstrate magnetic and hyperthermia properties of CoxFe3-xO4 (x = 0, 0.1, 0.3 and 0.5) nanoparticles synthesized via a simple cation exchange reaction of ˜12 nm Fe3O4 nanoparticles. The substitution of Fe cations with Co2+ ions leads to enhanced magnetocrystalline anisotropy and coercivity of the pristine superparamagnetic Fe3O4 nanoparticles. Hyperthermia measurement shows that by controlling the Co content (x = 0 to 0.5) in CoxFe3-xO4 nanoparticles, their specific absorption rate (SAR) can be greatly improved from 132 to 534 W/g. The strong enhancement in SAR value is attributed to the increased anisotropy and coercivity. Moreover, with the increase of ac magnetic field from 184 to 491 Oe, the SAR values of Fe3O4 and Co0.5Fe2.5O4 nanoparticles increase from 81 to 132 W/g and 220 to 534 W/g, respectively.

Nanosheets of oxides and hydroxides: Ultimate 2D charge-bearing functional crystallites.

PubMed

Ma, Renzhi; Sasaki, Takayoshi

2010-12-01

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.

Selective retention of basic compounds by metal aquo-ion affinity chromatography.

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks.

PubMed

Carmona, Francisco J; Rojas, Sara; Sánchez, Purificación; Jeremias, Hélia; Marques, Ana R; Romão, Carlos C; Choquesillo-Lazarte, Duane; Navarro, Jorge A R; Maldonado, Carmen R; Barea, Elisa

2016-07-05

The encapsulation of the photoactive, nontoxic, water-soluble, and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorganic porous matrixes, namely, the metalorganic framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiological conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiological conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degradation of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the solution.

Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

PubMed

Lin, Jian; Bao, Hongliang; Qie, Meiying; Silver, Mark A; Yue, Zenghui; Li, Xiaoyun; Zhu, Lin; Wang, Xiaomei; Zhang, Linjuan; Wang, Jian-Qiang

2018-06-05

Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO 4 )(H 2 O) 4 Cl]Cl·H 2 O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO 4 )(H 2 O) 4 Cl] + with Cl - as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th 4+ center in TMC are vulnerable to competition with F - , due to the formation of more favorable Th-F bonds compared to Th-OH 2 . This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.

Exchangeable hydrogen explains the pH of spodosol Oa horizons

USGS Publications Warehouse

Ross, D.S.; David, M.B.; Lawrence, G.B.; Bartlett, R.J.

1996-01-01

The chemistry of extremely acid Oa horizons does not conform to traditional pH, Al, and base saturation relationships. Results from two separate studies of northeastern U.S. forested soils were used to investigate relationships between pH in water or dilute salt solutions and other soil characteristics. In Oa horizons with pH below 4, soil pH in dilute CaCl2 solution was correlated with exchangeable H+ measured either by titration (r = -0.88, P = 0.0001, n = 142) or by electrode (r = -0.89, P = 0.0001, n = 45). Exchangeable H+ expressed as a percentage of the cation-exchange capacity (CEC) was linear with pH and showed similar slopes for data from both studies. For all samples, pHw = 4.21 - 1.80 x H+/CEC (R2 = 0.69, n = 194). The reciprocal of the H+/CEC ratio is base saturation with Al added to the bases. Because of the low pH, exchangeable Al does not appear to behave as an acid. Exchangeable H+ remains an operationally defined quantity because of the difficulty in separating exchange and hydrolysis reactions. In a variety of neutral-salt extractants, concentration of H+ were correlated with 0.1 M BaCl2-exchangeable H+ (r > 0.91, P = 0.0001, n = 26) regardless of the strength of the extract. Nine successive extractions with 0.33 mM CaCl2 removed more H+ than was removed by single batch extractions with either 1 M KCl or 0.1 M BaCl2 (average H+ of 70, 43, and 49 mmol kg-1, respectively for 26 samples). The data showed little difference in the chemical behavior of Oa horizons from a variety of geographical sites and vegetation types.

Two-dimensional solid-phase extraction strategy for the selective enrichment of aminoglycosides in milk.

PubMed

Shen, Aijin; Wei, Jie; Yan, Jingyu; Jin, Gaowa; Ding, Junjie; Yang, Bingcheng; Guo, Zhimou; Zhang, Feifang; Liang, Xinmiao

2017-03-01

An orthogonal two-dimensional solid-phase extraction strategy was established for the selective enrichment of three aminoglycosides including spectinomycin, streptomycin, and dihydrostreptomycin in milk. A reversed-phase liquid chromatography material (C 18 ) and a weak cation-exchange material (TGA) were integrated in a single solid-phase extraction cartridge. The feasibility of two-dimensional clean-up procedure that experienced two-step adsorption, two-step rinsing, and two-step elution was systematically investigated. Based on the orthogonality of reversed-phase and weak cation-exchange procedures, the two-dimensional solid-phase extraction strategy could minimize the interference from the hydrophobic matrix existing in traditional reversed-phase solid-phase extraction. In addition, high ionic strength in the extracts could be effectively removed before the second dimension of weak cation-exchange solid-phase extraction. Combined with liquid chromatography and tandem mass spectrometry, the optimized procedure was validated according to the European Union Commission directive 2002/657/EC. A good performance was achieved in terms of linearity, recovery, precision, decision limit, and detection capability in milk. Finally, the optimized two-dimensional clean-up procedure incorporated with liquid chromatography and tandem mass spectrometry was successfully applied to the rapid monitoring of aminoglycoside residues in milk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Carbonates by Spectral Induced Polarization

NASA Astrophysics Data System (ADS)

Hupfer, Sarah; Halisch, Matthias; Weller, Andreas

2017-04-01

This study investigates the complex electrical conductivity of carbonate samples by Spectral Induced Polarization (SIP). The analysis is conducted in combination with petrophysical, mineralogical and geochemical measurements. SIP is a useful tool to obtain more detailed information about rock properties and receive a more qualitative pore space characterization. Rock parameters like permeability, pore-size and -surface area can be predicted. Up to this point, sandstones or sandy materials were investigated in detail by laboratory SIP-measurements. Several robust empirical relationships were found that connect IP-signals and petrophysical parameters (surface area, surface conductivity and cation exchange capacity). Different types of carbonates were analyzed with laboratory SIP-measurements. Rock properties like grain density, porosity, permeability and surface area were determined by petrophysical measurements. Geochemistry and mineralogy were used to differentiate the carbonate types. First results of the SIP-measurements showed polarization effects for all different types. Four different phase behavior were observed in the phase spectra. A constant phase angle, a constant slope, a combination of both and a maximum type could be identified. Each phase behavior can be assigned to the specific carbonate type used, but the constant phase occurs at two carbonate types. Further experiments were conducted to get more insight the phase behavior and get explanations. 1. Approach: An expected phase peak frequency for each sample was calculated to check if this frequency is within the measured spectrum of 2 mHz to 100 Hz. 2. Approach: Significantly reducing of the fluid conductivity to increase phase signal for a better interpretation. 3. Approach: The cation-exchange-capacity (CEC) was regarded as a factor as well. A dependence between imaginary part of conductivity and CEC was detected. 4. Approach: Imaging procedures (scanning electron microscope, x-ray computed tomography, microscopy) were used to create a qualitative image of the carbonate samples and to investigate the pore space, for example the ratio of connected to non-connected pore space. A comparison between SIP data and the petrophysical data of the sample set showed that the phase behavior of carbonates is highly complicated and challenging compared with sandstones. It seems that there is no correlation between polarization effects and any petrophysical parameter. Ongoing investigations and measurements will be conducted to get more insight to the polarization effects of carbonates.

Preparation of catalysts via ion-exchangeable coatings on supports

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed are: new catalytic compositions which comprise an inert support coated with a hydrous alkali metal, alkaline earth metal, or quaternary ammonium titanate, niobate, zirconate, or tantalate, in which the alkali or alkaline earth metal or quaternary ammonium cations have been exchanged for a catalytically effective quantity of a catalytically effective metal.

Hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, Robert G.; Stephens, Howard P.

1990-01-01

A catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchange with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Porous Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, Fred

2005-01-01

This document is a slide presentation that examines the use of a simple templating process to produce hollow ceramic spheres with a pore size of 1 to 10 microns. Using ion exchange process it was determined that the method produces porous ceramic spheres with a unique structure: (i.e., inner sphere surrounded by an outer sphere.)

Ion-Exchanged SAPO-34 membranes for Krypton-Xenon Separation: Control of Permeation Properties and Fabrication of Hollow Fiber Membranes

DOE PAGES

Kwon, Yeon Hye; Min, Byunghyun; Yang, Shaowei; ...

2018-01-29

Separation of radioisotope 85Kr from 136Xe is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO- 34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance, via thickness reduction based upon control of a steam-assisted vapor-solid conversion technique followed by ion exchange with alkali metal cations. The reduction of membrane thickness leads to a large increase in Kr permeance from 7.5 gas permeation units (GPU) to 26.3 GPU with ideal Kr/Xe selectivities > 20 at 298 K. Cation-exchanged membranes show largemore » (>50%) increases in selectivity at ambient or slight sub-ambient conditions. The adsorption, diffusion, and permeation characteristics of ionexchanged SAPO-34 materials and membranes are investigated in detail, with potassium exchanged SAPO-34 membranes showing particularly attractive performance. Lastly, we then demonstrate the fabrication of selective SAPO-34 membranes on α-alumina hollow fibers.« less

Ion-Exchanged SAPO-34 membranes for Krypton-Xenon Separation: Control of Permeation Properties and Fabrication of Hollow Fiber Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, Yeon Hye; Min, Byunghyun; Yang, Shaowei

Separation of radioisotope 85Kr from 136Xe is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO- 34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance, via thickness reduction based upon control of a steam-assisted vapor-solid conversion technique followed by ion exchange with alkali metal cations. The reduction of membrane thickness leads to a large increase in Kr permeance from 7.5 gas permeation units (GPU) to 26.3 GPU with ideal Kr/Xe selectivities > 20 at 298 K. Cation-exchanged membranes show largemore » (>50%) increases in selectivity at ambient or slight sub-ambient conditions. The adsorption, diffusion, and permeation characteristics of ionexchanged SAPO-34 materials and membranes are investigated in detail, with potassium exchanged SAPO-34 membranes showing particularly attractive performance. Lastly, we then demonstrate the fabrication of selective SAPO-34 membranes on α-alumina hollow fibers.« less

Variation in whole DNA methylation in red maple (Acer rubrum) populations from a mining region: association with metal contamination and cation exchange capacity (CEC) in podzolic soils.

PubMed

Kalubi, K N; Mehes-Smith, M; Spiers, G; Omri, A

2017-04-01

Although a number of publications have provided convincing evidence that abiotic stresses such as drought and high salinity are involved in DNA methylation reports on the effects of metal contamination, pH, and cation exchange on DNA modifications are limited. The main objective of the present study is to determine the relationship between metal contamination and Cation exchange capacity (CEC) on whole DNA modifications. Metal analysis confirms that nickel and copper are the main contaminants in sampled sites within the Greater Sudbury Region (Ontario, Canada) and liming has increased soil pH significantly even after 30 years following dolomitic limestone applications. The estimated CEC values varied significantly among sites, ranging between 1.8 and 10.5 cmol(+) kg -1 , with a strong relationship being observed between CEC and pH (r = 0.96**). Cation exchange capacity, significantly lower in highly metal contaminated sites compared to both reference and less contaminated sites, was higher in the higher organic matter limed compared to unlimed sites. There was a significant variation in the level of cytosine methylation among the metal-contaminated sites. Significant and strong negative correlations between [5mdC]/[dG] and bioavailable nickel (r = -0.71**) or copper (r = -0.72**) contents were observed. The analysis of genomic DNA for adenine methylation in this study showed a very low level of [6N-mdA]/dT] in Acer rubrum plants analyzed ranging from 0 to 0.08%. Significant and very strong positive correlation was observed between [6N-mdA]/dT] and soil bioavailable nickel (r = 0.78**) and copper (r = 0.88**) content. This suggests that the increased bioavailable metal levels associated with contamination by nickel and copper particulates are associated with cytosine and adenine methylation.

Impacts of simulated acid rain on recalcitrance of two different soils.

PubMed

Dai, Zhongmin; Liu, Xingmei; Wu, Jianjun; Xu, Jianming

2013-06-01

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H2SO4 plus HNO3 at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH 2.0, whereas only cation exchange occurred above SAR pH 3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K(+) and Mg(2+) ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca(2+) >K(+) >Mg(2+) >Na(+) for the Plinthudult and Ca(2+) >Mg(2+) >Na(+) >K(+) for the Paleudalfs soil. The SARs above pH 3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH 2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.

The role of nonmagnetic d{sup 0} vs. d{sup 10}B-type cations on the magnetic exchange interactions in osmium double perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Hai L., E-mail: Hai.Feng@cpfs.mpg.de; Yamaura, Kazunari; Tjeng, Liu Hao

Polycrystalline samples of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were synthesized by solid state reactions. They adopt the cubic double perovskite structures (space group, Fm-3m) with ordered B and Os arrangements. Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) show antiferromagnetic transitions at 93 K, 69 K, and 28 K, respectively. The Weiss-temperatures are −590 K for Ba{sub 2}ScOsO{sub 6}, −571 K for Ba{sub 2}YOsO{sub 6}, and −155 K for Ba{sub 2}InOsO{sub 6}. Sc{sup 3+} and Y{sup 3+} have the open-shell d{sup 0} electronic configuration, while In{sup 3+} has the closed-shell d{sup 10}. This indicates that a d{sup 0} B-typemore » cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. Comparison of Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) to their Sr and Ca analogues shows that the structural distortions weaken the overall magnetic exchange interactions. - Graphical abstract: Magnetic properties of osmium double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. Comparison of Ba{sub 2}BOsO{sub 6}indicates that a d{sup 0} B-type cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. - Highlights: • Magnetic properties of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. • A d{sup 0}B-type cation induces stronger magnetic interactions than a d{sup 10}. • Structural distortions weaken the overall Os{sup 5+}-Os{sup 5+} magnetic interactions.« less

Evidence for a SN2-type pathway in the exchange of phosphines at a [PhSe]+ centre.

PubMed

Forfar, Laura C; Green, Michael; Haddow, Mairi F; Hussein, Sharifa; Lynam, Jason M; Slattery, John M; Russell, Christopher A

2015-01-07

A range of thio- and seleno-phosphonium cationic complexes [RE(PR'3)](+)[X](-) (R = Me, Ph; E = S, Se; X = GaCl4, SbF6) have been synthesised and structurally characterised. Reaction of [PhSPPh3][GaCl4] and [PhSePPh3][GaCl4] with P(t)Bu3 results in the ready transfer of the "RS(+)" and "RSe(+)" fragments from PPh3 to the stronger electron donor P(t)Bu3. NMR experiments combined with an Eyring analysis on the corresponding degenerate phosphine exchange reaction allowed the thermodynamic values for the phosphine exchange reaction of the sulfur cation (ΔH(‡) 18.7 ± 12.0 kJ mol(-1); ΔS(‡) -99.3 ± 36.3 J mol(-1) K(-1)) to be compared with the corresponding values (ΔH(‡) 2.4 ± 1.1 kJ mol(-1) and ΔS(‡) -58.1 ± 5.0 J mol(-1) K(-1)) for the [PhSePPh3](+) system. Importantly, the large negative entropy of activation and linear dependence on the rate of exchange are compatible with an SN2-type exchange process. This conclusion is supported by DFT calculations which confirm that the phosphine exchange process occurs via an associative mechanism. The rate of exchange was found to increase from sulfur to selenium and those with aryl substituents underwent exchange faster than those with alkyl substituents.

Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature

NASA Astrophysics Data System (ADS)

Hansch, Markus; Hämisch, Benjamin; Schweins, Ralf; Prévost, Sylvain; Huber, Klaus

2018-01-01

The dilute solution behavior of sodium poly(styrene sulfonate) is studied in the presence of trivalent Al3+ and bivalent Ba2+ cations at various levels of excess NaCl. The study evaluates the phase behavior and the morphology of the polyelectrolyte chains with increasing extent of decoration with the Al3+ and Ba2+ cations and analyses the effect of temperature on these decorated chains. The phase behavior is presented in the form of the cation concentration versus the respective poly(styrene sulfonate) concentration, recorded at the onset of precipitation. Whereas poly(styrene sulfonate) with Al3+ exhibits a linear phase boundary, denoted as the "threshold line," which increases with increasing poly(styrene sulfonate) concentration, Ba2+ cations show a threshold line which is independent of the poly(styrene sulfonate) concentration. An additional re-entrant phase, at considerably higher cation content than those of the threshold lines, is observed with Al3+ cations but not with Ba2+ cations. The threshold line and the re-entrant phase boundary form parts of the liquid-liquid phase boundary observed at the limit of low polymer concentration. The dimensions of the polyelectrolyte chains shrink considerably while approaching the respective threshold lines on increase of the Al3+ and Ba2+ cation content. However, subtle differences occur between the morphological transformation induced by Al3+ and Ba2+. Most strikingly, coils decorated with Al3+ respond very differently to temperature variations than coils decorated with Ba2+ do. As the temperature increases, the poly(styrene sulfonate) chains decrease their size in the presence of Al3+ cations but increase in size in the presence of Ba2+ cations.

Impact of managed moorland burning on peat nutrient and base cation status

NASA Astrophysics Data System (ADS)

Palmer, Sheila; Gilpin, Martin; Wearing, Catherine; Johnston, Kerrylyn; Holden, Joseph; Brown, Lee

2013-04-01

Controlled 'patch' burning of moorland vegetation has been used for decades in the UK to stimulate growth of heather (Calluna vulgaris) for game bird habitat and livestock grazing. Typically small patches (300-900 m2) are burned in rotations of 8-25 years. However, our understanding of the short-to-medium term environmental impacts of the practice on these sensitive upland areas has so far been limited by a lack of scientific data. In particular the effect of burning on concentrations of base cations and acid-base status of these highly organic soils has implications both for ecosystem nutrient status and for buffering of acidic waters. As part of the EMBER project peat chemistry data were collected in ten upland blanket peat catchments in the UK. Five catchments were subject to a history of prescribed rotational patch burning. The other five catchments acted as controls which were not subject to burning, nor confounded by other detrimental activities such as drainage or forestry. Soil solution chemistry was also monitored at two intensively studied sites (one regularly burned and one control). Fifty-centimetre soil cores, sectioned into 5-cm intervals, were collected from triplicate patches of four burn ages at each burned site, and from twelve locations at similar hillslope positions at each control site. At the two intensively monitored sites, soil solution chemistry was monitored at four depths in each patch. Across all sites, burned plots had significantly smaller cation exchange capacities, lower concentrations of exchangeable base cations and increased concentrations of exchangeable H+ and Al3+ in near-surface soil. C/N ratios were also lower in burned compared to unburned surface soils. There was no consistent trend between burn age and peat chemistry across all burned sites, possibly reflecting local controls on post-burn recovery rates or external influences on burn management decisions. At the intensively monitored site, plots burned less than two years prior to sampling had significantly smaller exchange capacities and lower concentrations of soil base cations in surface soils relative to plots burned 15-25 years previously. In contrast, surface soil solutions in recently burned plots were enriched in base cations relative to older plots and relative to the control site, possibly due to enhanced leaching at bare soil surfaces. The results offer evidence for an impact of burning on peat nutrient and acid-base status, but suggest that soils recover given time with no further burning.

The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

NASA Astrophysics Data System (ADS)

Limtrakul, J.; Kuno, M.; Treesukol, P.

1999-11-01

Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

Ab-initio calculation for cation vacancy formation energy in anti-fluorite structure

NASA Astrophysics Data System (ADS)

Saleel, V. P. Saleel Ahammad; Chitra, D.; Veluraja, K.; Eithiraj, R. D.

2018-04-01

Lithium oxide (Li2O) has been suggested as a suitable breeder blanket material for fusion reactors. Li+ vacancies are created by neutron irradiation, forming bulk defect complex whose extra character is experimentally unclear. We present a theoretical study of Li2O using density functional theory (DFT) with a plane-wave basis set. The generalized gradient approximation (GGA) and local-density approximation (LDA) were used for exchange and correlation. Here we address the total energy for defect free, cation defect, cation vacancy and vacancy formation energy in Li2O crystal in anti-fluorite structure.

A post audit and inverse modeling in reactive transport: 50 years of artificial recharge in the Amsterdam Water Supply Dunes

NASA Astrophysics Data System (ADS)

Karlsen, R. H.; Smits, F. J. C.; Stuyfzand, P. J.; Olsthoorn, T. N.; van Breukelen, B. M.

2012-08-01

SummaryThis article describes the post audit and inverse modeling of a 1-D forward reactive transport model. The model simulates the changes in water quality following artificial recharge of pre-treated water from the river Rhine in the Amsterdam Water Supply Dunes using the PHREEQC-2 numerical code. One observation dataset is used for model calibration, and another dataset for validation of model predictions. The total simulation time of the model is 50 years, from 1957 to 2007, with recharge composition varying on a monthly basis and the post audit is performed 26 years after the former model simulation period. The post audit revealed that the original model could reasonably predict conservative transport and kinetic redox reactions (oxygen and nitrate reduction coupled to the oxidation of soil organic carbon), but showed discrepancies in the simulation of cation exchange. Conceptualizations of the former model were inadequate to accurately simulate water quality changes controlled by cation exchange, especially concerning the breakthrough of potassium and magnesium fronts. Changes in conceptualization and model design, including the addition of five flow paths, to a total of six, and the use of parameter estimation software (PEST), resulted in a better model to measurement fit and system representation. No unique parameter set could be found for the model, primarily due to high parameter correlations, and an assessment of the predictive error was made using a calibration constrained Monte-Carlo method, and evaluated against field observations. The predictive error was found to be low for Na+ and Ca2+, except for greater travel times, while the K+ and Mg2+ error was restricted to the exchange fronts at some of the flow paths. Optimized cation exchange coefficients were relatively high, especially for potassium, but still within the observed range in literature. The exchange coefficient for potassium agrees with strong fixation on illite, a main clay mineral in the area. Optimized CEC values were systematically lower than clay and organic matter contents indicated, possibly reflecting preferential flow of groundwater through the more permeable but less reactive aquifer parts. Whereas the artificial recharge initially acted as an intrusion of relatively saline water triggering Na+ for Ca2+ exchange, further increasing total hardness of the recharged water, the gradual long-term reduction in salinity of the river Rhine since the mid 1970s has shifted to an intrusion of fresher water causing Ca2+ for Na+ exchange. As a result, seasonal and longer term reversal of the initial cation exchange processes was observed adding to the general long-term reduction in total hardness of the recharged Rhine water.

A universal mechanism for transport and regulation of CPA sodium proton exchangers.

PubMed

Călinescu, Octavian; Fendler, Klaus

2015-09-01

Recent studies performed on a series of Na+/H+ exchangers have led us to postulate a general mechanism for Na+/H+ exchange in the monovalent cation/proton antiporter superfamily. This simple mechanism employs a single binding site for which both substrates compete. The developed kinetic model is self-regulatory, ensuring down-regulation of transport activity at extreme pH, and elegantly explains the pH-dependent activity of Na+/H+ exchangers. The mechanism was experimentally verified and shown to describe both electrogenic and electroneutral exchangers. Using a small number of parameters, exchanger activity can be modeled under different conditions, providing insights into the physiological role of Na+/H+ exchangers.

Phase behavior in quaternary ammonium ionic liquid-propanol solutions: Hydrophobicity, molecular conformations, and isomer effects

NASA Astrophysics Data System (ADS)

Abe, Hiroshi; Kohki, Erica; Nakada, Ayumu; Kishimura, Hiroaki

2017-07-01

In ionic liquids (ILs), the effects of a quaternary ammonium cation containing a hydroxyl group were investigated and compared with the effect of a standard quaternary ammonium cation. The cation possessing a hydroxyl group is choline, Chol+, and the anion is bis(trifluoromethylsulfonyl)imide, TFSI-. Crystal polymorphism of pure [Chol][TFSI] was observed upon both cooling and heating by simultaneous X-ray diffraction and differential scanning calorimetry measurements. In contrast, [N3111][TFSI] (N3111+: N-trimethyl-N-propylammonium), a standard IL, demonstrated simple crystallization upon cooling. By adding 1-propanol or 2-propanol, the phase behaviors of the [Chol][TFSI]-based and [N3111][TFSI]-based mixtures were clearly distinguished. By Raman spectroscopy, the TFSI- anion conformers in the liquid state were shown to vary according to the propanol concentration, propanol isomer, and type of cation. The anomalous behaviors of pure [Chol][TFSI] and its mixtures are derived from hydrogen bonding of the hydroxyl group of Chol+ cation coupled with the hydrophobicity and packing efficiency of propanol.

Synthesis and characterization of 12-aminolauric acid-modified montmorillonite for catalytic application

NASA Astrophysics Data System (ADS)

Pagtalunan, Cris Angelo M.; Sumera, Florentino C.; Conato, Marlon T.

2018-05-01

The simple cation-exchange preparation of 12-aminolauric acid-modified montmorillonite (ALA-Mt), an aluminosilicate clay modified with the alkylammonium surfactant, is reported. Different loadings of 12-aminolauric acid (12-ALA) from 100 to 400 times the cation exchange capacity (CEC) in montmorillonite (Mt) was prepared and studied. Successful intercalation of the organic surfactant was monitored by the increase in basal (d001) spacing of the organoclay compared to the pure Mt. The clay mineral composite have increased surfactant loading resulting to lower degradation temperatures, rougher surface morphology, increased particle size, and increased organophilicity of the organoclay compared to the native Mt. The improved properties of ALA-Mt present it as an attractive catalyst material for polymerization reactions.

Process for removal of ammonia and acid gases from contaminated waters

DOEpatents

King, C. Judson; MacKenzie, Patricia D.

1985-01-01

Contaminating basic gases, i.e., ammonia, and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with steam, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

Process for removal of ammonia and acid gases from contaminated waters

DOEpatents

King, C.J.; Mackenzie, P.D.

1982-09-03

Contaminating basic gases, i.e., ammonia and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with stream, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

Phenolic cation exchange resin material for recovery of cesium and strontium

DOEpatents

Ebra, Martha A.; Wallace, Richard M.

1983-01-01

A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear waste solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs.sup.+ and Sr.sup.2+ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

Phenolic cation-exchange resin material for recovery of cesium and strontium. [Patent application

DOEpatents

Ebra, M.A.; Wallace, R.M.

1982-05-05

A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear wate solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs/sup +/ and Sr/sup 2 +/ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

A new approach to evaluate natural zeolite ability to sorb lead (Pb) from aqueous solutions

NASA Astrophysics Data System (ADS)

Drosos, Evangelos I. P.; Karapanagioti, Hrissi K.

2013-04-01

Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can significantly improve zeolite CEC by bringing the material to near homoionic form. pH and temperature are the critical parameters for using natural zeolites as sorbents. Zeolites should not be used in extremely acidic, neither in extremely basic pH conditions, except for very short times. The exchange of Pb, requires low solution pH, to avoid precipitation but not too low because the H+ are competitive ions for ion exchange; as a result the zeolite CEC related to Pb removal may be downgraded. If pH enters the basic range (e.g. pH>8), more aquatic complexes with lower positive valence than those prevailing in lower pH are produced; these complexes are less attracted by the negative charged zeolitic matrix. Pb uptake is favored at higher temperatures as ion exchange (including the diffusion of exchangeable ions inside the material and the medium, and vice versa) is an endothermic process. With the increase of temperature there is a decrease in hydration of all available exchangeable cations that eases the movement within the channels of the solid matrix. Additionally, the mobility of the potassium ions, present in the zeolitic material, also increases with the temperature resulting in enhanced CEC.

Impact of spreading olive mill waste water on agricultural soils for leaching of metal micronutrients and cations.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2017-07-01

Olive mill waste water (OMWW) is an acidic (pH 4-5), saline (EC ∼ 5-10 mS cm -1 ), blackish-red aqueous byproduct of the three phase olive oil production process, with a high chemical oxygen demand (COD) of up to 220,000 mg L -1 . OMWW is conventionally disposed of by uncontrolled dumping into the environment or by semi-controlled spreading on agricultural soils. It was hypothesized that spreading such liquids on agricultural soils could result in the release and mobilization of indigenous soil metals. The effect of OMWW spreading on leaching of metal cations (Na, K, Mg, Mn, Fe, Cu, Zn) was tested in four non-contaminated agricultural soils having different textures (sand, clay loam, clay, and loam) and chemical properties. While the OMWW contributed metals to the soil solution, it also mobilized indigenous soil metals as a function of soil clay content, cation exchange capacity (CEC), and soil pH-buffer capacity. Leaching of soil-originated metals from the sandy soil was substantially greater than from the loam and clay soils, while the clay loam was enriched with metals derived from the OMWW. These trends were attributed to cation exchange and organic-metal complex formation. The organic matter fraction of OMWW forms complexes with metal cations; these complexes may be mobile or precipitate, depending on the soil chemical and physical environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Active synthetic soil

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Henninger, Donald L. (Inventor); Allen, Earl R. (Inventor); Golden, Dadigamuwage C. (Inventor)

1995-01-01

A synthetic soil/fertilizer for horticultural application having all the agronutrients essential for plant growth is disclosed. The soil comprises a synthetic apatite fertilizer having sulfur, magnesium, and micronutrients dispersed in a calcium phosphate matrix, a zeolite cation exchange medium saturated with a charge of potassium and nitrogen cations, and an optional pH buffer. Moisture dissolves the apatite and mobilizes the nutrient elements from the apatite matrix and the zeolite charge sites.

Active synthetic soil

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Henninger, Donald L. (Inventor); Golden, Dadigamuwage C. (Inventor); Allen, Earl R. (Inventor)

1995-01-01

A synthetic soil/fertilizer for horticultural application having all the agronutrients essential for plant growth is disclosed. The soil comprises a synthetic apatite fertilizer having sulfur, magnesium and micronutrients dispersed in a calcium phosphate matrix, a zeolite cation exchange medium saturated with a charge of potassium and nitrogen cations, and an optional pH buffer. Moisture dissolves the apatite and mobilizes the nutrient elements from the apatite matrix and the zeolite charge sites.

Effects of climate, land management, and sulfur deposition on soil base cation supply in national forests of the southern Appalachian mountains

Treesearch

T.C. McDonnell; T.J. Sullivan; B.J. Cosby; W.A. Jackson; K.J. Elliott

2013-01-01

Forest soils having low exchangeable calcium (Ca) and other nutrient base cation (BC) reserves may induce nutrient deficiencies in acid-sensitive plants and impact commercially important tree species. Past and future depletion of soil BC in response to acidic sulfur (S) deposition, forest management, and climate change alter the health and productivity of forest trees...

Efficient Removal of Cationic and Anionic Radioactive Pollutants from Water Using Hydrotalcite-Based Getters.

PubMed

Bo, Arixin; Sarina, Sarina; Liu, Hongwei; Zheng, Zhanfeng; Xiao, Qi; Gu, Yuantong; Ayoko, Godwin A; Zhu, Huaiyong

2016-06-29

Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

Natural zeolite reactivity towards ozone: the role of compensating cations.

PubMed

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Improved hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed is a catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchanged with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Method of storing radioactive wastes using modified tobermorite

DOEpatents

Komarneni, Sridhar; Roy, Della M.

1985-01-01

A new cation exchanger is a modified tobermorite containing aluminum isomorphously substituted for silicon and containing sodium or potassium. The exchanger is selective for lead, rubidium, cobalt and cadmium and is selective for cesium over calcium or sodium. The tobermorites are compatable with cement and are useful for the long-term fixation and storage of radioactive nuclear wastes.

Heterodimerization of Arabidopsis calcium/proton exchangers contributes to regulation of guard cell dynamics and plant defense responses

USDA-ARS?s Scientific Manuscript database

"Arabidopsis thaliana" cation exchangers (CAX1 and CAX3) are closely related tonoplast-localized calcium/proton (Ca(2+)/H+) antiporters that contribute to cellular Ca(2+) homeostasis. CAX1 and CAX3 were previously shown to interact in yeast; however, the function of this complex in plants has remain...

Method of purifying neutral organophosphorus extractants

DOEpatents

Horwitz, E. Philip; Gatrone, Ralph C.; Chiarizia, Renato

1988-01-01

A method for removing acidic contaminants from neutral mono and bifunctional organophosphorous extractants by contacting the extractant with a macroporous cation exchange resin in the H.sup.+ state followed by contact with a macroporous anion exchange resin in the OH.sup.- state, whereupon the resins take up the acidic contaminants from the extractant, purifying the extractant and improving its extraction capability.

Wet and dry deposition in the AOSR collected by ion exchange resin samplers

Treesearch

Mark Fenn

2015-01-01

Atmospheric deposition of nitrogen (N), sulfur (S), and base cations was measured across the network of jack pine sites in the Athabasca Oil Sands Region using ion exchange resin (IER) collectors. Deposition was measured in forest clearings (bulk deposition) and under jack pine canopies (throughfall). As noted previously for other pollutants, throughfall deposition of...

Chemical restrictions of roots in Ultisol subsoils lessened by long-term management

NASA Technical Reports Server (NTRS)

Hardy, D. H.; Raper, C. D. Jr; Miner, G. S.; Raper CD, J. r. (Principal Investigator)

1990-01-01

Exchangeable Al in subsoils of Ultisols in the southeastern USA can restrict rooting depth. Downward movement of basic cations (Ca, Mg, and K), applied as lime and fertilizer, may diminish that restriction over time. Materials from the argillic horizon were collected from three paired sites, having managed (long-term cropping) and nonmanaged topsoils (Typic Paleudults and Hapludults). One managed site was cropped continuously for 15 yr while the others were cultivated for more than 30 yr. Concentrations of extractable cations and other nutrients from the paired sites were compared to determine the magnitude of change due to management. The ability of the subsoils to support plant growth was evaluated in a missing-nutrient greenhouse experiment with sorghum [Sorghum bicolor (L.) Moench]. Subsoils of managed sites had greater effective cation-exchange capacity (CEC) and base saturation than those of non-managed sites. While availabilities of Ca, Mg, and K in subsoils of nonmanaged sites were inadequate to support maximal plant growth, they were adequate in subsoils of managed sites. Compared with nonmanaged sites, KCl-exchangeable Al in subsoils of managed sites was 23% lower at the 15-yr location and 65 and 100% lower at the two other locations. In the absence of lime, sorghum growth was almost totally inhibited on nonmanaged subsoils amended with optimum nutrients. On the managed subsoils, where 100, 65, and 23% of the nonmanaged exchangeable Al had been neutralized by topsoil fertilization and liming, growth reductions under the same conditions were 0, 50, and 100%, respectively. Thus, relatively long-term management had improved these Ultisol subsoils for root growth and development.

Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions

NASA Astrophysics Data System (ADS)

Hansch, Markus; Kaub, Hans Peter; Deck, Sascha; Carl, Nico; Huber, Klaus

2018-03-01

Dilute solutions of sodium poly(styrene sulfonate) (NaPSS) in the presence of Al3+, Ca2+, and Ba2+ were analysed by means of isothermal titration calorimetry (ITC) in order to investigate the heat effect of bond formation between those cations and the anionic SO3- residues of NaPSS. The selection of the cations was guided by the solution behavior of the corresponding PSS salts from a preceding study [M. Hansch et al., J. Chem. Phys. 148(1), 014901 (2018)], where bonds between Ba2+ and anionic PSS showed an increasing solubility with decreasing temperature and Al3+ exhibited the inverse trend. Unlike to Al3+ and Ba2+, Ca2+ is expected to behave as a purely electrostatically interacting bivalent cation and was thus included in the present study. Results from ITC satisfactorily succeeded to explain the temperature-dependent solution behavior of the salts with Al3+ and Ba2+ and confirmed the non-specific behavior of Ca2+. Additional ITC experiments with salts of Ca2+ and Ba2+ and sodium poly(acrylate) complemented the results on PSS by data from a chemically different polyanion. Availability of these joint sets of polyanion-cation combinations not only offers the chance to identify common features and subtle differences in the solution behavior of polyelectrolytes in the presence of multi-valent cations but also points to a new class of responsive materials.

Cation activation of the pig kidney sodium pump: transmembrane allosteric effects of sodium.

PubMed Central

Karlish, S J; Stein, W D

1985-01-01

We have studied activation by Na or Rb ions of different transport modes of the Na-K pump, using phospholipid vesicles reconstituted with pig kidney Na-K-ATPase. The shape of the activation curves, sigmoid or quasi-hyperbolic, depends on the nature of the cation at the opposite surface and not on the specific mode of transport. ATP-dependent Na uptake into K-containing vesicles (Na-K exchange) is activated by cytoplasmic Na along a highly sigmoid curve in the absence of extracellular Na (Hill number, nH = 1.9). Activation displays progressively less-sigmoid curves as extracellular Na is raised to 150 mM (nH = 1.2). The maximal rate of the Na-K exchange is not affected. Na is not transported from the extracellular face by the pump in the presence of excess extracellular K, and the transmembrane effects of the extracellular Na are therefore 'allosteric' in nature. ATP-dependent Na-Na exchange (Lee & Blostein, 1980) and classical ATP-plus-ADP-dependent Na-Na exchange are activated by cytoplasmic Na along hyperbolic curves. ATP-dependent Na uptake into Tris-containing vesicles is activated by cytoplasmic Na along a somewhat sigmoidal curve. (ATP + Pi)-dependent Rb-Rb exchange is activated by cytoplasmic and extracellular Rb along strictly hyperbolic curves. The same applies for Rb-Rb exchange in the presence or absence of ATP or Pi alone. The presence of a high concentration of extracellular Na together with extracellular Rb induces a sigmoidal activation by cytoplasmic Rb of (ATP + Pi)-dependent Rb-Rb exchange (nH = 1.45) but does not affect the maximal rate of exchange. Slow passive Rb fluxes through the pump observed in the absence of other pump ligands (see Karlish & Stein, 1982 alpha) are activated by cytoplasmic Rb along a strictly hyperbolic curve with extracellular Rb, nH = 1.0 (Rb-Rb exchange), along a strongly sigmoid curve with extracellular Na, nH = 1.5 (Rb-Na exchange), and along less-sigmoid curves with extracellular Tris, nH = 1.24 (net Rb flux) or extracellular Li, nH = 1.2 (Rb-Li exchange). Activation of the passive Rb fluxes by extracellular Rb is hyperbolic in the presence of cytoplasmic Rb, Li or Tris but is sigmoid in the presence of cytoplasmic Na (nH = 1.36). Inhibition by cytoplasmic Na of passive Rb fluxes from the cytoplasmic to the extracellular face of the pump depends on the nature of the cation at the extracellular surface.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:2582111

Inductively coupled plasma mass spectrometry study of the retention behavior of arsenic species on various solid phase extraction cartridges and its application in arsenic speciation

NASA Astrophysics Data System (ADS)

Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

2003-07-01

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate the retention behavior of arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), arsenocholine (AsC), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TMAI) on various silica-based solid phase extraction (SPE) cartridges. A method for arsenic speciation is then developed on the basis of selective SPE separation of arsenic species and highly sensitive ICP-MS detection. Factors affecting the retention and elution of arsenic species were examined. Results showed that the retention of arsenic species depended on the chemical characteristics of arsenic species and the types of sorbent materials. Change of pH in the range of 2.0-9.0 did not show significant effects on the retention of DMA, AsB, AsC, TMAI and TMAO on an ethylbenzene sulfonic acid-based strong cation exchange (SCX-3) cartridge. pH also did not influence the retention of AsB, AsC, TMAI and TMAO on a mixed-mode (M-M) cartridge containing non-polar, strong cation exchange and strong anion exchange (SAX) functional groups. However, the retentions of As(V) and MMA on the SAX and the M-M cartridge changed with pH. As(V) and MMA were completely retained on the SAX cartridge and sequentially selectively eluted with 1.0 mol l -1 acetic acid (for MMA). DMA, AsB, AsC, TMAI and TMAO were completely retained on the SCX-3 cartridge and sequentially selectively eluted with 1.0 mol l -1 HNO 3 (for DMA). As(V), MMA, AsB, AsC, TMAI and TMAO were completely retained on the M-M cartridge. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently determined by ICP-MS. A detection limit of 8 ng l -1 arsenic in water sample was obtained. This method was successfully applied to arsenic speciation in various sources of water samples (drinking water, waste water, raw water, etc.) and US National Institute of Standards and Technology standard reference materials with good precision and accuracy.

Development of a Waste Water Regenerative System - Using Sphagnum Moss Ion-exchange

NASA Astrophysics Data System (ADS)

McKeon, M.; Wheeler, R.; Leahy, Jj

The use of inexpensive, light weight and regenerative systems in an enclosed environment is of great importance to sustained existence in such habitats as the International Space Station, Moon or even Mars. Many systems exist which utilise various synthetic ion exchangers to complete the process of waste water clean-up. These systems do have a very good exchange rate for cations but a very low exchange rate for anions. They also have a maximum capacity before they need regeneration. This research proposes a natural alternative to these synthetic ion-exchangers that utilises one of natures greatest ion-exchangers, that of Sphagnum Moss. Sphagna can be predominantly found in the nutrient poor environment of Raised Bogs, a type of isolated wetland with characteristic low pH and little interaction with the surrounding water table. All nutrients come from precipitation. The sphagna have developed as the bog's sponges, soaking up all available nutrients (both cation & anion) from the precipitation and eventually distributing them to the surrounding flora and fauna, through the water. The goal of this research is to use this ability in the processing of waste water from systems similar to isolated microgravity environments, to produce clean water for reuse in these environments. The nutrients taken up by the sphagna will also be utilised as a growth medium for cultivar growth, such as those selected for hydroponics' systems.

Effect of experimental variables onto Co(2+) and Sr(2+) sorption behavior in red mud-water suspensions.

PubMed

Milenković, Aleksandra S; Smičiklas, Ivana D; Šljivić-Ivanović, Marija Z; Živković, Ljiljana S; Vukelić, Nikola S

2016-07-02

The prospects of rinsed red mud (alumina production residue) utilization for liquid radioactive waste treatment have been investigated, with Co(2+) and Sr(2+) as model cations of radioactive elements. To evaluate the sorption effectiveness and corresponding binding mechanisms, the process was analyzed in batch conditions, by varying experimental conditions (pH, Co(2+) and Sr(2+) concentrations in single solutions and binary mixtures, contact time, and the concentration of competing cations and ligands common in liquid radioactive waste). Comparison of the Co(2+) and Sr(2+) sorption pH edges with the red mud isoelectric point has revealed that Co(2+) removal took place at both positive and negative red mud surface, while Sr(2+) sorption abruptly increased when the surface became negatively charged. The increase of initial cation content and pH resulted in increased equilibrium times and sorption capacity and decreased rate constants. From single metal solutions and various binary mixtures, Co(2+) was sorbed more efficiently and selectively than Sr(2+). While Sr(2+) sorption was reduced by coexisting cations in the order Al(3+) ≥ Ca(2+) >Na(+) ≥Cs(+), removal of Co(2+) was affected by Al(3+) species and complexing agents (EDTA and citrate). Desorption of Co(2+) was negligible in Ca(2+) and Sr(2+) containing media and in solutions with initial pH 4-7. Sr(2+) desorption was generally more pronounced, especially at low pH and in the presence of Co(2+). Collected macroscopic data signify that Co(2+) sorption by red mud minerals occurred via strong chemical bonds, while Sr(2+) was retained mainly by weaker ion-exchange or electrostatic interactions. Results indicate that the rinsed red mud represent an efficient, low-cost sorbent for Co(2+) and Sr(2+) immobilization.

Layered inorganic/organic mercaptopropyl pendant chain hybrid for chelating heavy cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Macedo, Thais R.; Petrucelli, Giovanni C.; Pinto, Alane A.

2011-12-15

Graphical abstract: Crystalline lamellar silicate RUB-18 was immobilized with mercaptopropyl groups at the surface and then used as support for cadmium and lead removal from aqueous solutions. Highlights: Black-Right-Pointing-Pointer Synthetic methodology requires intercalation. Black-Right-Pointing-Pointer Organofunctionalized ilerite compound as sorbent. Black-Right-Pointing-Pointer Active mercaptopropyl groups remove cations. Black-Right-Pointing-Pointer High maximum sorption capacity for cadmium. -- Abstract: Heavy metal sorbents with uptake capacities for divalent cadmium and lead cation removal from aqueous solutions have been synthesized by grafting mercaptopropyltrimethoxysilane onto the surface of two different precursors obtained from lamellar ilerite, its acidic and the cetyltrimethylammonium exchanged forms. The organofunctionalization was carried out bymore » two different procedures: reflux and solvent evaporation methodologies. Elemental analysis data based on carbon content gave 1.37 and 3.53 mmol of organic pendant groups per gram of hybrid by the reflux method, when starting from acidic ilerite and the surfactant form. X-ray diffraction corroborated the maintenance of the original crystallinity. Infrared spectroscopy and nuclear magnetic resonance for {sup 29}Si and {sup 13}C nuclei are in agreement with the success of the proposed method. The sulfur basic centers attached to the lamellar structure are used to coordinate both cations at the solid/liquid interface. The isotherms were obtained through the batchwise process and the experimental data were adjusted to the Freundlich model. The maximum sorption capacities of 5.55 and 5.12 mmol g{sup -1} for lead and 6.10 and 7.10 mmol g{sup -1} for cadmium were obtained for organofunctionalized ilerite and its surfactant form, synthesized by reflux methodology. This behavior suggested that these hybrids could be employed as promising sorbents with a polluted system.« less

Interplay of bonding and geometry of the adsorption complexes of light alkanes within cationic faujasites. Combined spectroscopic and computational study.

PubMed

Pidko, Evgeny A; Xu, Jiang; Mojet, Barbara L; Lefferts, Leon; Subbotina, Irina R; Kazansky, Vladimir B; van Santen, Rutger A

2006-11-16

A FT-IR spectroscopic study of methane, ethane, and propane adsorption on magnesium and calcium forms of zeolite Y reveals different vibrational properties of the adsorbed molecules depending on the exchanged cation. This is attributed to different adsorption conformations of the hydrocarbons. Two-fold eta(2) coordination of light alkanes is realized for MgY, whereas in case of CaY zeolite quite different adsorption modes are found, involving more C-H bonds in the interaction with the cation. The topological analysis of the electron density distribution function of the adsorption complexes shows that when a hydrocarbon coordinates to the exchanged Mg(2+) ions, van der Waals bonds between H atoms of the alkane and basic zeolitic oxygens significantly contribute to the overall adsorption energy, whereas in case of CaY zeolite such interactions play only an indirect role. It is found that, due to the much smaller ionic radius of the Mg(2+) ion as compared to that of Ca(2+), the former ions are significantly shielded with the surrounding oxygens of the zeolitic cation site. This results in a small electrostatic contribution to the stabilization of the adsorbed molecules. In contrast, for CaY zeolite the stabilization of alkanes in the electrostatic field of the partially shielded Ca(2+) cation significantly contributes to the adsorption energy. This is in agreement with the experimentally observed lower overall absorption of C-H stretching vibrations of alkanes loaded to MgY as compared to those for CaY zeolite. The preferred conformation of the adsorbed alkanes is controlled by the bonding within the adsorption complexes that, in turn, strongly depends on the size and location of the cations in the zeolite cavity.

Conformations of cationized linear oligosaccharides revealed by FTMS combined with in-ESI H/D exchange.

PubMed

Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

2015-10-01

Previously (Kostyukevich et al. Anal Chem 2014, 86, 2595), we have reported that oligosaccharides anions are produced in the electrospray in two different conformations, which differ by the rate of gas phase hydrogen/deuterium (H/D) exchange reaction. In the present paper, we apply the in-electrospray ionization (ESI) source H/D exchange approach for the investigation of the oligosaccharides cations formed by attaching of metal ions (Na, K) to the molecule. It was observed that the formation of different conformers can be manipulated by varying the temperature of the desolvating capillary of the ESI interphase. Separation of the conformers was performed using gas phase H/D approach. Because the conformers have different rates of the H/D exchange reaction, the deuterium distribution spectrum becomes bimodal. It was found that the conformation corresponding to the slow H/D exchange rate dominates in the spectrum when the capillary temperature is low (~200 °C), and the conformation corresponding to the fast H/D exchange rate dominates at high (~400 °C) temperatures. In the intermediate temperature region, two conformers are present simultaneously. It was also observed that large oligosaccharide requires higher temperature for the formation of another conformer. It was found that the presence of the conformers considerably depends on the solvent used for ESI and the pH. We have compared these results with the previously performed in-ESI source H/D exchange experiments with peptides and proteins. Copyright © 2015 John Wiley & Sons, Ltd.

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

New cation-exchange material based on a sulfonated 3,4-ethylenedioxythiophene monomer

NASA Astrophysics Data System (ADS)

Stéphan, O.; Schottland, P.; Le Gall, P.-Y.; Chevrot, C.

1998-06-01

The electrochemical oxidation, in aqueous medium, of a 3,4-ethylenedioxythiophene monomer functionalized by a sulfonate group exhibiting cation-exchange properties, allows the synthesis of a new type of water-soluble material. In order to synthesize in water, by oxidative electropolymerization, polymer films of controlled thickness containing attached sulfonate groups, we have investigated the polymerization of the functionalized monomer in the presence of the unsubstituted one without supporting electrolyte. Using an equimolar mixture (0.01 mol/l) of both monomers, copolymers exhibiting cation exchange abilities have been synthesized. As an example, th easy incorporation of hexaamine-ruthenium(III) into one of these copolymers is briefly reported. L'oxydation électrochimique en milieu aqueux d'un monomère de type 3,4- éthylènedioxythiophène fonctionnalisé par un groupement sulfonate permet d'envisager la synthèse d'un nouveau type de polymère hydrosoluble. Afin d'obtenir électrochimiquement en milieu aqueux, un film de polymère d'épaisseur contrôlée contenant des groupements sulfonates, nous avons evisagé de polymériser ce monomère en présence de son homologue non substitué. En partant d'un mélange équimolaire (0.01 mol/l) des deux monomères et en l'absence d'électrolyte support, nous avons synthétisé un matériau possédant des propriétés d'échange de cations. A titre d'exemple, nous présentons brièvement l'incorporation d'un complexe hexaaminé du ruthénium(III) dans un de ces copolymères.

Synthesis and Characterization of Organic-Inorganic Nanocomposite Poly-o-anisidine Sn(IV) Arsenophosphate: Its Analytical Applications as Pb(II) Ion-Selective Membrane Electrode

PubMed Central

Khan, Asif Ali; Habiba, Umme; Khan, Anish

2009-01-01

Poly-o-anisidine Sn(IV) arsenophosphate is a newly synthesized nanocomposite material and has been characterized on the basis of its chemical composition, ion exchange capacity, TGA-DTA, FTIR, X-RAY, SEM, and TEM studies. On the basis of distribution studies, the exchanger was found to be highly selective for lead that is an environmental pollutant. For the detection of lead in water a heterogeneous precipitate based ion-selective membrane electrode was developed by means of this composite cation exchanger as electroactive material. The membrane electrode is mechanically stable, with a quick response time, and can be operated over a wide pH range. The selectivity coefficients were determined by mixed solution method and revealed that the electrode is sensitive for Pb(II) in presence of interfering cations. The practical utility of this membrane electrode has been established by employing it as an indicator electrode in the potentiometric titration of Pb(II). PMID:20140082

Organotin-mediated exchange diffusion of anions in human red cells

PubMed Central

1979-01-01

Organotin cations (R3Sn+) form electrically neutral ion pairs with monovalent anions. It is demonstrated that the tin derivatives induce exchange diffusion of chloride in red cells and resealed ghosts, without any detectable increase of membrane permeability to net movements of chloride ions. The obligatory anion exchange is believed to be due to the permeation of electroneural ion pairs, whereas the organic cation (R3Sn+) has an extremely low membrane permeability. Exchange fluxes of chloride increased with the lipophilicity of the substituting group (R3). At the same molar concentration of organotin, the relative potencies of the tin derivatives as anion carriers (with trimethyltin as a reference) were: methyl 1, ethyl 30, propyl = phenyl 1,00, and butyl 10,000. Tributyltin-mediated anion exchange was studied in detail. The organotin-induced anion transport increased through the sequence: F- less than Cl- less than Br- less than I- = SCN- less than OH-. Partitioning of tributyltin into red cell membranes was greater in iodide than in chloride media (partition coefficients 6.6 and 1.7 x 10(- 3) cm, respectively). Bicarbonate, fluoride, nitrate, phosphate, and sulphate did not exchange with chloride in the presence of tributyltin. Chloride exchange fluxes increased linearly with tributylin concentrations up to 10(-5) M, and with chloride concentrations up to at least 0.9 M. The apparent turnover number for tributyltin-mediated chloride exchange increased from 15 to 1,350 s-1 between 0 and 38 degrees C. These figures are minimum turnover numbers, because it is not known what fraction of the organotin in the membrane exists as chloride ion pairs. PMID:479814

Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide-copper sulfide heterostructured nanorods.

PubMed

Zheng, Haimei; Sadtler, Bryce; Habenicht, Carsten; Freitag, Bert; Alivisatos, A Paul; Kisielowski, Christian

2013-11-01

The atomic structure and interfaces of CdS/Cu2S heterostructured nanorods are investigated with the aberration-corrected TEAM 0.5 electron microscope operated at 80 kV and 300 kV applying in-line holography and complementary techniques. Cu2S exhibits a low-chalcocite structure in pristine CdS/Cu2S nanorods. Under electron beam irradiation the Cu2S phase transforms into a high-chalcocite phase while the CdS phase maintains its wurtzite structure. Time-resolved experiments reveal that Cu(+)-Cd(2+) cation exchange at the CdS/Cu2S interfaces is stimulated by the electron beam and proceeds within an undisturbed and coherent sulfur sub-lattice. A variation of the electron beam current provides an efficient way to control and exploit such irreversible solid-state chemical processes that provide unique information about system dynamics at the atomic scale. Specifically, we show that the electron beam-induced copper-cadmium exchange is site specific and anisotropic. A resulting displacement of the CdS/Cu2S interfaces caused by beam-induced cation interdiffusion equals within a factor of 3-10 previously reported Cu diffusion length measurements in heterostructured CdS/Cu2S thin film solar cells with an activation energy of 0.96 eV. © 2013 Elsevier B.V. All rights reserved.

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

PubMed Central

Ye, Shi; Sun, Jiayi; Yi, Xiong; Wang, Yonggang; Zhang, Qinyuan

2017-01-01

Luminescent zeolites exchanged with two distinct and interacted emissive ions are vital but less-studied for the potential applications in white light emitting diodes, solar cells, optical codes, biomedicine and so on. Typical transition metal ion Mn2+ and lanthanide ion Yb3+ are adopted as a case study via their characteristic transitions and the interaction between them. The option is considered with that the former with d-d transition has a large gap between the first excited state 4T1 and the ground state 6A1 (normally >17,000 cm−1) while the latter with f-f transition has no metastable excited state above 10,000 cm−1, which requires the vicinity of these two ions for energy transfer. The results of various characterizations, including BET measurement, photoluminescence spectroscopy, solid-state NMR, and X-ray absorption spectroscopy, etc., show that Yb3+ would preferably enter into the zeolite-Y pores and introduction of Mn2+ would cause aggregation of each other. Herein, cation-cation repulsion may play a significant role for the high valence of Mn2+ and Yb3+ when exchanging the original cations with +1 valence. Energy transfer phenomena between Mn2+ and Yb3+ occur only at elevated contents in the confined pores of zeolite. The research would benefit the design of zeolite composite opto-functional materials. PMID:28393920

An acid-free water-born quaternized chitosan/montmorillonite loaded into an innovative ultra-fine bead-free water-born nanocomposite nanofibrous scaffold; in vitro and in vivo approaches.

PubMed

Dastjerdi, Roya; Sharafi, Mahsa; Kabiri, Kourosh; Mivehi, Leila; Samadikuchaksaraei, Ali

2017-07-26

An acid-free water-born chitosan derivative/montmorillonite has been successfully synthesized. A natural-based biopolymer, N-(2-hydroxy) propyl-3-trimethyl ammonium chitosan chloride, was synthesized, and its structure confirmed by Fourier transform infrared microscopy and conductometric titration. It was applied to the cationic ion-exchange reaction of montmorillonite. Then, the synthesized materials were used to produce water-born composite scaffolds for tissue engineering applications and formed an ultra-fine bead-free multicomponent nanofibrous scaffold. The scaffold was subjected to in vitro and in vivo investigations. The effects of both acidic and neutral reaction media on the efficiency of the cationic ion-exchange reaction of montmorillonite were investigated. A mechanism has been suggested for the more efficient cationic ion-exchange reaction achieved in the absence of the acid. In in vitro studies, the modified montmorillonite showed synergistic biocompatibility and cell growth with enhanced bioactivity compared to unmodified clay and even chitosan and the chitosan derivative. Scanning electron microscopy showed ultra-fine bead-free nanocomposite nanofibers. Improved biocompatibility, cell attachment, and cell growth were observed for the nanofibrous scaffolds compared to the individual components. In vivo experiments showed complete restoration of a critical-sized full-thickness wound without infection in 21 d. The technique provides a guideline to achieve chitosan nanofibrous morphology for multifunctional biomedical applications.

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

NASA Astrophysics Data System (ADS)

Ye, Shi; Sun, Jiayi; Yi, Xiong; Wang, Yonggang; Zhang, Qinyuan

2017-04-01

Luminescent zeolites exchanged with two distinct and interacted emissive ions are vital but less-studied for the potential applications in white light emitting diodes, solar cells, optical codes, biomedicine and so on. Typical transition metal ion Mn2+ and lanthanide ion Yb3+ are adopted as a case study via their characteristic transitions and the interaction between them. The option is considered with that the former with d-d transition has a large gap between the first excited state 4T1 and the ground state 6A1 (normally >17,000 cm-1) while the latter with f-f transition has no metastable excited state above 10,000 cm-1, which requires the vicinity of these two ions for energy transfer. The results of various characterizations, including BET measurement, photoluminescence spectroscopy, solid-state NMR, and X-ray absorption spectroscopy, etc., show that Yb3+ would preferably enter into the zeolite-Y pores and introduction of Mn2+ would cause aggregation of each other. Herein, cation-cation repulsion may play a significant role for the high valence of Mn2+ and Yb3+ when exchanging the original cations with +1 valence. Energy transfer phenomena between Mn2+ and Yb3+ occur only at elevated contents in the confined pores of zeolite. The research would benefit the design of zeolite composite opto-functional materials.

Water reuse in the l-lysine fermentation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsiao, T.Y.; Glatz, C.E.

1996-02-05

L-Lysine is produced commercially by fermentation. As is typical for fermentation processes, a large amount of liquid waste is generated. To minimize the waste, which is mostly the broth effluent from the cation exchange column used for l-lysine recovery, the authors investigated a strategy of recycling a large fraction of this broth effluent to the subsequent fermentation. This was done on a lab-scale process with Corynebacterium glutamicum ATCC 21253 as the l-lysine-producing organisms. Broth effluent from a fermentation in a defined medium was able to replace 75% of the water for the subsequent batch; this recycle ratio was maintained formore » 3 sequential batches without affecting cell mass and l-lysine production. Broth effluent was recycled at 50% recycle ratio in a fermentation in a complex medium containing beet molasses. The first recycle batch had an 8% lower final l-lysine level, but 8% higher maximum cell mass. In addition to reducing the volume of liquid waste, this recycle strategy has the additional advantage of utilizing the ammonium desorbed from the ion-exchange column as a nitrogen source in the recycle fermentation. The major problem of recycling the effluent from the complex medium was in the cation-exchange operation, where column capacity was 17% lower for the recycle batch. The loss of column capacity probably results from the buildup of cations competing with l-lysine for binding.« less

A transferable force field for CdS-CdSe-PbS-PbSe solid systems

NASA Astrophysics Data System (ADS)

Fan, Zhaochuan; Koster, Rik S.; Wang, Shuaiwei; Fang, Changming; Yalcin, Anil O.; Tichelaar, Frans D.; Zandbergen, Henny W.; van Huis, Marijn A.; Vlugt, Thijs J. H.

2014-12-01

A transferable force field for the PbSe-CdSe solid system using the partially charged rigid ion model has been successfully developed and was used to study the cation exchange in PbSe-CdSe heteronanocrystals [A. O. Yalcin et al., "Atomic resolution monitoring of cation exchange in CdSe-PbSe heteronanocrystals during epitaxial solid-solid-vapor growth," Nano Lett. 14, 3661-3667 (2014)]. In this work, we extend this force field by including another two important binary semiconductors, PbS and CdS, and provide detailed information on the validation of this force field. The parameterization combines Bader charge analysis, empirical fitting, and ab initio energy surface fitting. When compared with experimental data and density functional theory calculations, it is shown that a wide range of physical properties of bulk PbS, PbSe, CdS, CdSe, and their mixed phases can be accurately reproduced using this force field. The choice of functional forms and parameterization strategy is demonstrated to be rational and effective. This transferable force field can be used in various studies on II-VI and IV-VI semiconductor materials consisting of CdS, CdSe, PbS, and PbSe. Here, we demonstrate the applicability of the force field model by molecular dynamics simulations whereby transformations are initiated by cation exchange.

Cadmium uptake by Pinus resinosa Ait. pollen and the effect on cation release and membrane permeability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strickland, R.C.; Chaney, W.R.; Lamoreaux, R.J.

Cadmium uptake by red pine (Pinus resinosa Ait.) pollen from a graded series of Cd/sup 2 +/ solutions (0 to 2.88 microequivalents per 50 milligrams pollen) and its effect on membrane integrity were examined by atomic absorption spectroscopy. Uptake was strongly dependent on Cd/sup 2 +/ concentration and was limited to adsorption and cation exchange in pollen walls during a 3-hour measurement period. Good correlation between measured Cd/sup 2 +/ uptake and that predicted by the Langmuir and Freundlich isotherm equations indicated the adsorptive nature of Cd/sup 2 +/ uptake. While substantial quantities of Ca/sup 2 +/ and Mg/sup 2more » +/ were released by exchange mechanisms concurrent with Cd/sup 2 +/ uptake, there was no evidence for leakage of cations due to membrane impairment as indicated by a poor correlation between Cd/sup 2 +/ uptake and K/sup +/ efflux. Virtually all Cd/sup 2 +/ removed from solution was freely exchangeable with 0.5 millimolar CaCl/sub 2/ and demonstrated that Cd/sup 2 +/ did not readily enter pine pollen but was adsorbed on the pollen wall. Ultraviolet transmission spectra of treatment solutions and analyses of phosphate and reducing sugar efflux also indicated that the potent toxicity of Cd/sup 2 +/ to pollen germination and germ tube elongation was not the result of membrane damage.« less

Large-scale synthesis of lead telluride (PbTe) nanotube-based nanocomposites with tunable morphology, crystallinity and thermoelectric properties

NASA Astrophysics Data System (ADS)

Park, Kee-Ryung; Cho, Hong-Baek; Song, Yoseb; Kim, Seil; Kwon, Young-Tae; Ryu, Seung Han; Lim, Jae-Hong; Lee, Woo-Jin; Choa, Yong-Ho

2018-04-01

A few millimeter-long lead telluride (PbTe) hollow nanofibers with thermoelectric properties was synthesized for the first time with high through manner via three-step sequential process of electrospinning, electrodeposition and cationic exchange reaction. As-synthesized electrospun Ag nanofibers with ultra-long aspect ratio of 10,000 were Te electrodeposited to obtain silver telluride nanotubes and underwent cationic exchange reaction in Pb(NO3)2 solution to obtain polycrystalline PbTe nanotubes with average diameter of 100 nm with 20 nm of wall thickness. Variation of the Ag-to-Pb ratio in the AgxTey-PbTe nanocomposites during the cationic exchange reaction enabled to control the thermoelectric properties of resulting 1D hollow nanofibers. The diameter of Ag nanofiber is the key factor to determine the final dimension of the PbTe nanotubes in the topotactic transformation and the content of Ag ion leads to the enhancement of thermoelectric properties in the AgxTey-PbTe nanocomposites. The synthesized 1D nanocomposite mats showed the highest value of Seebeck coefficient of 433 μV/K (at 300 K) when the remained Ag content was 30%, while the power factor reached highest to 0.567 μW/mK2 for the pure PbTe nanotubes. The enhancement of thermoelectric properties and the composite crystallinity are elucidated with relation to Ag contents in the resulting 1D nanocomposites.

Quantum dot impregnated-chitosan film for heavy metal ion sensing and removal.

PubMed

Jaiswal, Amit; Ghsoh, Siddhartha Sankar; Chattopadhyay, Arun

2012-11-06

We report the use of biopolymer-stabilized ZnS quantum dots (Q-dots) for cation exchange reaction-based easy sensing and removal of heavy metal ions such as Hg(2+), Ag(+), and Pb(2+) in water. Chitosan-stabilized ZnS Q-dots were synthesized in aqueous medium and were observed to have been converted to HgS, Ag(2)S, and PbS Q-dots in the presence of corresponding ions. The transformed Q-dots showed characteristic color development, with Hg(2+) being exceptionally identifiable due to the visible bright yellow color formation, while brown coloration was observed in other metal ions. The cation exchange was driven by the difference in the solubility product of the reactant and the product Q-dots. The cation exchanged Q-dots preserved the morphology of the reactant Q-dots and displayed volume increase based on the bulk crystal lattice parameters. The band gap of the transformed Q-dots showed a major increase from the corresponding bulk band gap of the material, demonstrating the role of quantum confinement. Next, we fabricated ZnS Q-dot impregnated chitosan film which was used to remove heavy metal ions from contaminated water as measured using atomic absorption spectroscopy (AAS). The present system could suitably be used as a simple dipstick for elimination of heavy metal ion contamination in water.

Comparison of gaseous oxidized Hg measured by KCl-coated denuders, and nylon and cation exchange membranes.

PubMed

Huang, Jiaoyan; Miller, Matthieu B; Weiss-Penzias, Peter; Gustin, Mae Sexauer

2013-07-02

The chemical compounds that make up gaseous oxidized mercury (GOM) in the atmosphere, and the reactions responsible for their formation, are not well understood. The limitations and uncertainties associated with the current method applied to measure these compounds, the KCl-coated denuder, are not known due to lack of calibration and testing. This study systematically compared the uptake of specific GOM compounds by KCl-coated denuders with that collected using nylon and cation exchange membranes in the laboratory and field. In addition, a new method for identifying different GOM compounds using thermal desorption is presented. Different GOM compounds (HgCl2, HgBr2, and HgO) were found to have different affinities for the denuder surface and the denuder underestimated each of these compounds. Membranes measured 1.3 to 3.7 times higher GOM than denuders in laboratory and field experiments. Cation exchange membranes had the highest collection efficiency. Thermodesorption profiles for the release of GOM compounds from the nylon membrane were different for HgO versus HgBr2 and HgCl2. Application of the new field method for collection and identification of GOM compounds demonstrated these vary as a function of location and time of year. Understanding the chemistry of GOM across space and time has important implications for those developing policy regarding this environmental contaminant.

Multivariate statistical analysis and hydrogeochemical modelling of seawater-freshwater mixing along selected flow paths: Case of Korba coastal aquifer Tunisia

NASA Astrophysics Data System (ADS)

Slama, Fairouz; Bouhlila, Rachida

2017-11-01

Groundwater sampling and piezometric measurements were carried out along two flow paths (corresponding to two transects) in Korba coastal plain (Northeast of Tunisia). The study aims to identify hydrochemical processes occurring when seawater and freshwater mix. Those processes can be used as indicators of seawater intrusion progression and freshwater flushing into seawater accompanying Submarine Groundwater Discharge (SGD). Seawater fractions in the groundwater were calculated using the chloride concentration. Hierarchical cluster analysis (HCA) was applied to isolate wells potentially affected by seawater. In addition, PHREEQC was used to simulate the theoretical mixing between two end members: seawater and a fresh-brackish groundwater sample. Geochemical conventional diagrams showed that the groundwater chemistry is explained by a mixing process between two end members. Results also revealed the presence of other geochemical processes, correlated to the hydrodynamic flow paths. Direct cation exchange was linked to seawater intrusion, and reverse cation exchange was associated to the freshwater flushing into seawater. The presence of these processes indicated that seawater intrusion was in progress. An excess of Ca, that could not be explained by only cation exchange processes, was observed in both transects. Dedolomitization combined to gypsum leaching is the possible explanation of the groundwater Ca enrichment. Finally, redox processes were also found to contribute to the groundwater composition along flow paths.

Location and ion-binding of membrane-associated valinomycin, a proton nuclear magnetic resonance study.

PubMed

Meers, P; Feigenson, G W

1988-03-03

Valinomycin, incorporated in small unilamellar vesicles of perdeuterated dimyristoylphosphatidylcholine, reveals several well-resolved 1H-NMR resonances. These resonances were used to examine the location, orientation and ion-binding of membrane-bound valinomycin. The order of affinity of membrane-bound valinomycin for cations is Rb+ greater than K+ greater than Cs+ greater than Ba2+, and binding is sensitive to surface change. The exchange between bound and free forms is fast on the NMR time scale. The intrinsic binding constants, extrapolated to zero anion concentration, are similar to those determined in aqueous solution. Rb+ and K+ show 1:1 binding to valinomycin, whereas the stoichiometry of Cs+ and Ba2+ is not certain. Paramagnetic chemical shift reagents and nitroxide spin label relaxation probes were used to study the location and orientation of valinomycin in the membrane. Despite relatively fast exchange of bound cations, the time average location of the cation-free form of valinomycin is deep within the bilayer under the conditions of these experiments. Upon complexation to K+, valinomycin moves closer to the interfacial region.

A new type of polyhedron-based metal-organic frameworks with interpenetrating cationic and anionic nets demonstrating ion exchange, adsorption and luminescent properties.

PubMed

Zhang, Zheng-Jie; Shi, Wei; Niu, Zheng; Li, Huan-Huan; Zhao, Bin; Cheng, Peng; Liao, Dai-Zheng; Yan, Shi-Ping

2011-06-14

An interesting new MOF, built with interpenetrating cationic (MOF-A(+)) and anionic (MOF-B(-)) nets that do not require counter ions to balance charge, together with an architectural strategy focused on the use of MOPs as nodes and MOCs as spacers for the generation of 3D frameworks, is reported. This journal is © The Royal Society of Chemistry 2011

Titanate-based adsorbents for radioactive ions entrapment from water.

PubMed

Yang, Dongjiang; Liu, Hongwei; Zheng, Zhanfeng; Sarina, Sarina; Zhu, Huaiyong

2013-03-21

This feature article reviews some titanate-based adsorbents for the removal of radioactive wastes (cations and anions) from water. At the beginning, we discuss the development of the conventional ion-exchangeable titanate powders for the entrapment of radioactive cations, such as crystalline silicotitanate (CST), monosodium titanate (MST), peroxotitanate (PT). Then, we specially emphasize the recent progress in the uptake of radioactive ions by one-dimensional (1D) sodium titanate nanofibers and nanotubes, which includes the synthesis and phase transformation of the 1D nanomaterials, adsorption ability (capacity, selectivity, kinetics, etc.) of radioactive cations and anions, and the structural evolution during the adsorption process.

Hydroxide Degradation Pathways for Substituted Benzyltrimethyl Ammonium: A DFT Study

DOE PAGES

Long, Hai; Pivovar, Bryan S.

2014-11-01

The stability of cations used in the alkaline exchange membranes has been a major challenge. In this paper, degradation energy barriers were investigated by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations. Findings show that electron-donating substituent groups at meta-position(s) of the benzyl ring could result in increased degradation barriers. However, after investigating more than thirty substituted BTMA+ cations, the largest improvement in degradation barrier found was only 6.7 kJ/mol. This suggests a modest (8×) improvement in stability for this type of approach may be possible, but for anything greater other approaches will need to be pursued.

Suitability of the methylene blue test for determination of cation exchange capacity of clay minerals related to ammonium acetate method

NASA Astrophysics Data System (ADS)

Milošević, Maja; Logar, Mihovil; Dojčinović, Biljana; Erić, Suzana

2015-04-01

Cation exchange capacity (CEC) represents one of the most important parameters of clay minerals which reflects their ability to exchange cations with liquid phases in near contact. Measurement of CEC is used for characterizing sample plasticity, adsorbing and swelling properties which later define their usage in industrial purposes. Several methods have been developed over the years for determination of layer charge, charge density, charge distribution, etc. and have been published in numerous papers (Czimerova et al., 2006; Yukselen and Kaya, 2008). The main goal of present study is comparison of suitability of more recent method - methylene blue test in regard to older method - ammonium acetate for determination of CEC. For this study, we selected one montmorillonite clay (Bogovina, Serbia) and two mainly kaolinite clays (Miličinica, Serbia). Chemicals used for CEC determinations were solution of methylene blue (MB)(14*10-6M/ml) and ammonium acetate (AA) solution (1M). The obtained results are showing generally lower values in case of MB method. The main difference is due to molecular aggregation of MB on the clay surface. AA method is highly sensitive to the presence of CaO. Release of Ca ion from the sample into the solution can limit the saturation of exchange sites by the ammonium ion. This is clearly visible in case of montmorillonite clay. Fe2+ and Mg ions are difficult to move by the ammonium ion because of their ion radius, but in case of MB molecule there is no such restriction in removing them from the exchange sites. MB solution, even in a low concentration (2*10-6M/ml), is showing preferable results in moving the ions from their positions which is already visible after adding a small quantity of solution (25cm3). Both MB-titration and MB-spot test yield similar results and are much simpler methods than AA and they also give other information such as specific surface area (external and internal) whereas AA method only provides information about cations in exchangeable positions. Both methods, methylene blue test and ammonium acetate method, have advantages and disadvantages and differ in their requirements for the sample preparations but in general method selection is depending on the specific application of the given sample. References: - Yukselen, Y. and Kaya, A., Engineering Geology 102 (2008) 38-45 - Czimerova, A., Bujdak, J. and Dohrmann, R., Applied Clay Science 34 (2006) 2-13

Nature of the Interlayer Environment in an Organoclay Optimized for the Sequestration of Dibenzo-p-dioxin

EPA Science Inventory

A Na-smectite clay (Na-SWy-2) was exchanged with various amounts of dimethyldioctadecylammonium bromide (DODA-Br) up to twice the cation exchange capacity (CEC). The organoclay (DODA - SWy-2) with DODA-Br added at 2 X CEC exhibited a maximum 4.2 nm d-spacing and a 31.4% c...

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, S; DeSilva, MA; Brennecke, JF

2014-12-25

Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange processmore » between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.« less

TIE METHODS FOR TOXICITY EVALUATION OF FRESHWATER SEDIMENTS

EPA Science Inventory

Three toxicity identification evaluation (TIE) methods, AVS spiking, zero-valent metal and cation exchange resin, have been used with metal contaminated and enriched sediments to remove the toxicity...

Electroosmosis through a Cation-Exchange Membrane: Effect of an ac Perturbation on the Electroosmotic Flow.

PubMed

Barragán; Ruíz Bauzá C

2000-10-15

Electroosmosis experiments through a cation-exchange membrane have been performed using NaCl solutions in different experimental situations. The influence of an alternating (ac) sinusoidal perturbation, of known angular frequency and small amplitude, superimposed to the usual applied continuous (dc) signal on the electroosmotic flow has been studied. The experimental results show that the presence of the ac perturbation affects the electroosmotic flow value, depending on the frequency of the ac signal and on the solution stirring conditions. In the frequency range studied, two regions have been observed where the electroosmotic flow reaches a maximum value: one at low frequencies ( approximately Hz); and another at frequencies of the order of kHz. These regions could be related to membrane relaxation phenomena. Copyright 2000 Academic Press.

Surface segregation in binary mixtures of imidazolium-based ionic liquids

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2010-09-01

Surface composition of binary mixtures of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry at room temperature over a wide composition range. The imidazolium cations with longer aliphatic groups tend to segregate to the surface, and a bis(trifluoromethanesulfonyl)imide anion (Tf 2N -) is enriched at the surface relative to hexafluorophosphate (PF 6-). The surface of an equimolar mixture of Li[Tf 2N] and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6]) has a nominal composition of [bmim][Tf 2N] because of surface segregation and ligand exchange. The surface segregation of cations and anions is likely to result from alignment of specific ligand-exchanged molecules at the topmost surface layer to exclude more hydrophobic part of the molecules.

Material Removes Heavy Metal Ions From Water

NASA Technical Reports Server (NTRS)

Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

1995-01-01

New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

Separation of certain carboxylic acids utilizing cation exchange membranes

DOEpatents

Chum, H.L.; Sopher, D.W.

1983-05-09

A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100/sup 0/C and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

Separation of certain carboxylic acids utilizing cation exchange membranes

DOEpatents

Chum, Helena L.; Sopher, David W.

1984-01-01

A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100.degree. C. and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chibani, Siwar, E-mail: siwar.chibani@univ-lorraine.fr; Chebbi, Mouheb; Badawi, Michael, E-mail: michael.badawi@univ-lorraine.fr

The potential use of some cation-exchanged mordenite (H{sup +}, Na{sup +}, Cu{sup +}, and Ag{sup +}) as a selective adsorbent for volatile iodine species (ICH{sub 3} and I{sub 2}), which can be released during a nuclear accident together with a steam carrier gas, is investigated using density functional theory. It is found that in the case of Cu-MOR and Ag-MOR, the absolute values of interaction energies of ICH{sub 3} and I{sub 2} are higher than that of water which indicates that these forms of zeolite could be suitable for selective adsorption of iodine species. In contrast, the H-MOR and Na-MORmore » are found to be unsuitable for this purpose. A systematic investigation of all adsorption sites allowed us to analyze the structural effects affecting the adsorption behavior. For the Ag-MOR and Cu-MOR zeolites, the iodine compounds are adsorbed preferentially in the large channel of mordenite (main channel) while water prefers the small channel or the side pocket where it forms stronger hydrogen bonds. The factors governing the interaction energies between the cationic sites and the different molecules are analyzed and the important role of van der Waals interactions in these systems is highlighted.« less

Investigation of pharmaceutical transport in saturated sandy aquifers using column experiments: the effect of pH

NASA Astrophysics Data System (ADS)

Börnick, Hilmar; Boxberger, Norman; Licha, Tobias; Worch, Eckhard

2010-05-01

Due to the development of advanced analytical techniques it is increasingly known that a high number of polar organic trace compounds, particularly residues of pharmaceuticals, occur in the aquatic environment. In contrast to the sources and pathways of such compounds, their impact on ecosystems and their fate in different environmental compartments are comparatively less investigated. Because of the spatial extension and time available, the zone between water and natural solids (e.g. sediments or soil in groundwater zones, bank filtration sites and for soil aquifer treatment) plays an important role in the elimination of anthropogenic trace compounds from water phase. Here, degradation and sorption processes mainly influence the content of trace compounds. Correlations, specific for compound groups, between n-octanol-water distribution coefficients, available from experiment or calculations, and sorption coefficients (e.g. KOC) often allow a suitable prognosis of the transport behavior of organic pollutants in an underground passage. In case of polar, ionizable organic compounds such prediction is problematic and often not possible. Here, besides relatively weak non-polar van der Waals attraction, other interaction mechanisms, such as covalent bonding, complex formation, or ion exchange, can dominate. The latter is closely connected with the type of basic and/or acid groups in a molecule. The degree of protonation could be changed in dependence of type and concentration of other ions and of the acidity constants (pKa) and therefore from pH. Laboratory column studies at different pH value (range from 4 to 8) were carried out using natural sandy sediments from aquifers and model water containing selected pharmaceuticals to investigate the influence of degree of protonation on sorption. Eight different pharmaceuticals were chosen for laboratory column experiments. Their selection was based on the presence of basic/acid functional groups, pKa, high production and consumption rates, and occurrence in environment. The long-term objective of this research is to consider specific interactions such as ion exchange for the improved transport models. Breakthrough experiments show that retardation is significantly influenced by pH for the majority of the selected pharmaceuticals. As a general tendency, it was observed that a decreasing pH caused an enhanced delay. For acidic compounds such as naproxen, this behavior was expected because of the neutral species being the dominating one. The stronger retardation of cationic agents such as atenolol with decreased pH could be explained by additional cation exchange effects. With the exception of atenolol all chosen model compounds show a high stability towards microbial degradation at aerobic conditions. All experiments were repeated at least three times at identical conditions, whereby a good reproducibility was observed. Further experiments are currently performed to characterize pH-depending change of sediment surfaces and to investigate the competitive influence of other presented cations.

A simple graphical representation of selectivity in hydrophilic interaction liquid chromatography.

PubMed

Ibrahim, Mohammed E A; Liu, Yang; Lucy, Charles A

2012-10-19

This paper uses the HILIC selectivity data of Dinh et al. (J. Chromatogr. A 1218 (2011) 5880) to yield simple and easy to understand plots analogous to Neue plots for selectivity in HILIC. The plots categorize 21 previously studied HILIC phases (data from Dinh et al.), 8 additional HILIC columns and 4 reversed phase columns (our data) using selected probes for specific interactions. The relative retention of cytosine vs. uracil is used to probe the "hydrophilicity" of the HILIC phases; adenosine vs. adenine is used to probe the ability of the stationary phase to participate in hydrogen bonding; and benzyltrimethylammonium (BTMA) vs. cytosine is used to probe the cation exchange and anion exchange character of the column. Plots of kBTMA/kcytosine vs. kcytosine/kuracil successfully classify silica, amide, zwitterionic, diol and reverse phase columns in terms of their HILIC behavior. Polymeric columns including polymer substrate and polymer coated columns show low ion exchange character, but vary widely in their hydrophilicity. Alternatively a HILIC-Phase Selectivity Chart, in analogy to the Neue plot, is constructed by plotting log(kBTMA/kcytosine) vs. log(kcytosine). This plot enables classification of HILIC columns that will yield similar or significantly different separations. Copyright © 2012 Elsevier B.V. All rights reserved.

Testing the potential of geochemical techniques in identifying hydrological systems within landslides in partly weathered marls

NASA Astrophysics Data System (ADS)

Bogaard, T. A.

2003-04-01

This paper’s objectives are twofold: to test the potential of cation exchange capacity (CEC) analysis for refinement of the knowledge of the hydrological system in landslide areas; and to examine two laboratory CEC analysis techniques on their applicability to partly weathered marls. The NH4Ac and NaCl laboratory techniques are tested. The geochemical results are compared with the core descriptions and interpreted with respect to their usefulness. Both analysis techniques give identical results for CEC, and are plausible on the basis of the available clay content information. The determination of the exchangeable cations was more difficult, since part of the marls dissolved. With the ammonium-acetate method more of the marls are dissolved than with the sodium-chloride method. This negatively affects the results of the exchangeable cations. Therefore, the NaCl method is to be preferred for the determination of the cation fractions at the complex, be it that this method has the disadvantage that the sodium fraction cannot be determined. To overcome this problem it is recommended to try and use another salt e.g. SrCl2 as displacement fluid. Both Alvera and Boulc-Mondorès examples show transitions in cation composition with depth. It was shown that the exchangeable cation fractions can be useful in locating boundaries between water types, especially the boundary between the superficial, rain fed hydrological system and the lower, regional ground water system. This information may be important for landslide interventions since the hydrological system and the origin of the water need to be known in detail. It is also plausible that long-term predictions of slope stability may be improved by knowledge of the hydrogeochemical evolution of clayey landslides. In the Boulc-Mondorès example the subsurface information that can be extracted from CEC analyses was presented. In the Boulc-Mondorès cores deviant intervals of CEC could be identified. These are interpreted as weathered layers that may develop or have already developed into slip surfaces. The CEC analyses of the cores revealed ‘differences in chemical composition’ that can have an influence on slope stability. It is known that the chemical composition of a soil may have a large effect on the strength parameters of the material. The technique described here can also be used before core sampling for laboratory strength tests. The major problem of the CEC analyses turned out to be the explanation of the origin of the differences found in the core samples. From the above it is concluded that geochemistry is a potentially valuable technique for e.g. landslide research, but it is recognised that still a lot of work has to be done before the technique can be applied in engineering practice.

Effects of CaCO3 treatment on the morphology, crystallinity, rheology and hydrolysis of gelatinized maize starch dispersions.

PubMed

Garcia-Diaz, S; Hernandez-Jaimes, C; Escalona-Buendia, H B; Bello-Perez, L A; Vernon-Carter, E J; Alvarez-Ramirez, J

2016-09-15

Using calcium salts instead of lime allows for an ecological nixtamalization of maize grains, where the negative contamination impact of the traditional lime nixtamalization is reduced. This work assessed the effects of calcium carbonate (0.0-2.0%w/w CaCO3) on the morphology, crystallinity, rheology and hydrolysis of gelatinized maize starch dispersions (GMSD). Microscopy analysis showed that CaCO3 changed the morphology of insoluble remnants (ghosts) and decreased the degree of syneresis. Analysis of particle size distribution showed a slight shift to smaller sizes as the CaCO3 was increased. Also, X-ray patterns indicated that crystallinity achieved a minimum value at CaCO3 concentration in the range of 1%w/w. GMSD with higher CaCO3 concentrations exhibited higher thixotropy area and complex viscoelastic behavior that was frequency dependent. A possible mechanism involved in the starch chain modification by CaCO3 is that starch may act as a weak acid ion exchanger capable of exchanging alcoholic group protons for cations (Ca(+2)). Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of the mixed organic cation ratio in lead iodide based perovskite on the performance of solar cells.

PubMed

Salado, Manuel; Calio, Laura; Berger, Rüdiger; Kazim, Samrana; Ahmad, Shahzada

2016-10-05

Lead halide based perovskite solar cells are presently the flagship among the third generation solution-processed photovoltaic technologies. The organic cation part in the perovskite plays an important role in terms of crystal structure tuning from tetragonal to trigonal or pseudocubic or vice versa depending on the organic cations used, while it also displays different microstructure. In this paper, we demonstrate the influence of the organic cation part with respect to optical properties, hysteresis behavior, and stability. This study offers a clear understanding of the perovskite properties and how they can be modulated by compositional engineering. With a rational choice, light harvesting abilities and hysteresis behavior can be controlled in these systems. The substitution of formamidinium cation by methylammonium cation allows achieving low temperature annealing and inducing stability in perovskites together with enhanced photovoltaic properties. By the use of in-situ scanning force microscopy experiments the conversion of precursors to perovskite at a particular temperature can be visualized.

Illitization of Potassium, Cesium, and Ammonium Exchanged Smectite

NASA Astrophysics Data System (ADS)

Mills, M. M.; Wang, Y.; Payne, C.; Sanchez, A. C.; Boisvert, L.; Matteo, E. N.

2017-12-01

Bentonite clay is a primary choice for engineered barrier systems within geologic repositories for disposal of radioactive wastes due to its low permeability at saturated states, warranting diffusion as the dominant transport mechanism, and large swelling pressures that promote sealing. In order to predict how well the barrier will function over time at repository relevant temperatures, it is important to understand thermal alteration effects on montmorillonite, better known as smectite, a main constituent of bentonite. One type of thermal alteration is the conversion to illite, when exposed to elevated temperatures and a sufficient amount of potassium ions, thereby weakening barrier functions. To facilitate the conversion of smectite to illite and examine the influence of interlayer cations, illitization experiments on cation exchanged smectite were performed within hydrothermal reaction vessels over one week timescales. The <2um fraction of a Na-rich smectite clay was first exchanged with 1M Cs, K, and NH4 salt solutions and further exposed to hydrous pyrolysis using a 1M KCl solution with various solid to liquid ratios at 200°C. Multiple analysis techniques were used to characterize the altered clay and identify extent of conversion, such as XRD, cation exchange capacity, and morphology changes by SEM. The pore-water chemistry was also analyzed by ICP-OES to detect any dissolved products and silica content. Results suggest the conversion rate is relatively fast, occurring within days, and is dependent on not only the amount of K, but also dissolved silica concentration related to total solid in solution. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND2017-7856A

pH Lowering Ability of Sphagnum.

ERIC Educational Resources Information Center

Glime, Janice M.; Li, Yenhung

1998-01-01

States that the ecological role of Sphagnum species in peatlands is enormous. Presents a cation exchange experiment and background information on the characteristics and economic importance of Sphagnum. Contains 42 references. (DDR)

Investigating the Thermal Limit of Clay Minerals for Applications in Nuclear Waste Repository Design

NASA Astrophysics Data System (ADS)

Matteo, E. N.; Miller, A. W.; Kruichak, J.; Mills, M.; Tellez, H.; Wang, Y.

2013-12-01

Clay minerals are likely candidates to aid in nuclear waste isolation due to their low permeability, favorable swelling properties, and high cation sorption capacities. Establishing the thermal limit for clay minerals in a nuclear waste repository is a potentially important component of repository design, as flexibility of the heat load within the repository can have a major impact on the selection of repository design. For example, the thermal limit plays a critical role in the time that waste packages would need to cool before being transferred to the repository. Understanding the chemical and physical changes that occur in clay minerals at various temperatures above the current thermal limit (of 100 °C) can enable decision-makers with information critical to evaluating the potential trade-offs of increasing the thermal limit within the repository. Most critical is gaining understanding of how varying thermal conditions in the repository will impact radionuclide sorption and transport in clay materials either as engineered barriers or as disposal media. A variety of clays (illite, mixed layer illite/smectite, montmorillonite, and palygorskite) were heated for a range of temperatures between 100-500 °C. These samples were characterized by a variety of methods, including nitrogen adsorption, x-ray diffraction, thermogravimetric analysis, barium chloride exchange for cation exchange capacity (CEC), and iodide sorption. The nitrogen porosimetry shows that for all the clays, thermally-induced changes in BET surface area are dominated by collapse/creation of the microporosity, i.e. pore diameters < 17 angstroms. Changes in micro porosity (relative to no heat treatment) are most significant for heat treatments 300 °C and above. Alterations are also seen in the chemical properties (CEC, XRD, iodide sorption) of clays, and like pore size distribution changes, are most significant above 300 °C. Overall, the results imply that changes seen in pores size distribution correlate with cation exchange capacity and cation exchange processes. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's Nation Nuclear Security Administration under contract DE-AC04-94AL85000. SAND Number: 2013-6352A.

Analyzing Solutions High in Total Dissolved Solids for Rare Earth Elements (REEs) Using Cation Exchange and Online Pre-Concentration with the seaFAST2 Unit; NETL-TRS-7-2017; NETL Technical Report Series; U.S. Department of Energy, National Energy Technology Laboratory: Albany, OR, 2017; p 32

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, J.; Torres, M.; Verba, C.

The accurate quantification of the rare earth element (REE) dissolved concentrations in natural waters are often inhibited by their low abundances in relation to other dissolved constituents such as alkali, alkaline earth elements, and dissolved solids. The high abundance of these constituents can suppress the overall analytical signal as well as create isobaric interferences on the REEs during analysis. Waters associated with natural gas operations on black shale plays are characterized by high salinities and high total dissolved solids (TDS) contents >150,000 mg/L. Methods used to isolate and quantify dissolved REEs in seawater were adapted in order to develop themore » capability of analyzing REEs in waters that are high in TDS. First, a synthetic fluid based on geochemical modelling of natural brine formation fluids was created within the Marcellus black shale with a TDS loading of 153,000 mg/L. To this solution, 1,000 ng/mL of REE standards was added based on preliminary analyses of experimental fluids reacted at high pressure and temperature with Marcellus black shale. These synthetic fluids were then run at three different dilution levels of 10, 100, and 1,000–fold dilutions through cation exchange columns using AG50-X8 exchange resin from Eichrom Industries. The eluent from the cation columns were then sent through a seaFAST2 unit directly connected to an inductively coupled plasma mass spectrometer (ICP-MS) to analyze the REEs. Percent recoveries of the REEs ranged from 80–110% and fell within error for the external reference standard used and no signal suppression or isobaric interferences on the REEs were observed. These results demonstrate that a combined use of cation exchange columns and seaFAST2 instrumentation are effective in accurately quantifying the dissolved REEs in fluids that are >150,000 mg/L in TDS and have Ba:Eu ratios in excess of 380,000.« less

Hydroxide based Benzyltrimethylammonium degradation: Quantification of rates and degradation technique development

DOE PAGES

Sturgeon, Matthew R.; Macomber, Clay S.; Engtrakul, Chaiwat; ...

2015-01-21

Anion exchange membranes (AEMs) are of interest as hydroxide conducting polymer electrolytes in electrochemical devices like fuel cells and electrolyzers. AEMs require hydroxide stable covalently tetherable cations to ensure required conductivity. Benzyltrimethylammonium (BTMA) has been the covalently tetherable cation that has been most often employed in anion exchange membranes because it is reasonably basic, compact (limited number of atoms per charge), and easily/cheaply synthesized. Several reports exist that have investigated hydroxide stability of BTMA under specific conditions, but consistency within these reports and comparisons between them have not yet been made. While the hydroxide stability of BTMA has been believedmore » to be a limitation for AEMs, this stability has not been thoroughly reported. In this paper, we have found that several methods reported have inherent flaws in their findings due to the difficulty of performing degradation experiments at high temperature and high pH. In order to address these shortcomings, we have developed a reliable, standardized method of determining cation degradation under conditions similar/relevant to those expected in electrochemical devices. The experimental method has been employed to determine BTMA stabilities at varying cation concentrations and elevated temperatures, and has resulted in improved experimental accuracy and reproducibility. Finally and most notably, these results have shown that BTMA is quite stable at 80°C (half-life of ~4 years), a significant increase in stability over what had been reported previously.« less

Water quality monitoring of Jialing-River in Chongqing using advanced ion chromatographic system.

PubMed

Tanaka, Kazuhiko; Shi, Chao-Hong; Nakagoshi, Nobukazu

2012-04-01

The water quality monitoring operation to evaluate the water quality of polluted river is an extremely important task for the river-watershed management/control based on the environmental policy. In this study, the novel, simple and convenient water quality monitoring of Jialing-River in Chongqing, China was carried out using an advanced ion chromatography (IC) consisting of ion-exclusion/cation-exchange chromatography (IEC/CEC) with conductivity detection for determining simultaneously the common anions such as SO4(2-), Cl(-), and NO3(-) and the cations such as Na+, NH4+, K+, Mg2+, and Ca2+, the ion-exclusion chromatography (IEC) with visible detection for determining simultaneously the nutrient components such as phosphate and silicate ions, and the IEC with the enhanced conductivity detection using a post column of K+-form cation-exchange resin for determining HCO3(-)-alkalinity as an inorganic-carbon source for biomass synthesis in biological reaction process under the aerobic conditions. According to the ionic balance theory between the total equivalent concentrations of anions and cations, the water quality evaluation of the Jialing-River waters taking at different sampling sites in Chongqing metropolitan area was carried out using the advanced IC system. As a result, the effectiveness of this novel water quality monitoring methodology using the IC system was demonstrated on the several practical applications to a typical biological sewage treatment plant on Jialing-River of Chongqing.

Silver Dissolution and Release from Ceramic Water Filters.

PubMed

Mittelman, Anjuliee M; Lantagne, Daniele S; Rayner, Justine; Pennell, Kurt D

2015-07-21

Application of silver nanoparticles (nAg) or silver nitrate (AgNO3) has been shown to improve the microbiological efficacy of ceramic water filters used for household water treatment. Silver release, however, can lead to undesirable health effects and reduced filter effectiveness over time. The objectives of this study were to evaluate the contribution of nanoparticle detachment, dissolution, and cation exchange to silver elution, and to estimate silver retention under different influent water chemistries. Dissolved silver (Ag(+)) and nAg release from filter disks painted with 0.03 mg/g casein-coated nAg or AgNO3 were measured as a function of pH (5-9), ionic strength (1-50 mM), and cation species (Na(+), Ca(2+), Mg(2+)). Silver elution was controlled by dissolution as Ag(+) and subsequent cation exchange reactions regardless of the applied silver form. Effluent silver levels fell below the drinking water standard (0.1 mg/L) after flushing with 30-42 pore volumes of pH 7, 10 mM NaNO3 at pH 7. When the influent water was at pH 5, contained divalent cations or 50 mM NaNO3, silver concentrations were 5-10 times above the standard. Our findings support regular filter replacement and indicate that saline, hard, or acidic waters should be avoided to minimize effluent silver concentrations and preserve silver treatment integrity.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

PubMed

Kamcev, Jovan; Paul, Donald R; Manning, Gerald S; Freeman, Benny D

2017-02-01

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl 2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

Cesium-specific phenolic ion exchange resin

DOEpatents

Bibler, J.P.; Wallace, R.M.

1995-08-15

A phenolic, cesium-specific, cation exchange resin is prepared by neutralizing resorcinol with potassium hydroxide, condensing/polymerizing the resulting intermediate with formaldehyde, heat-curing the resulting polymer to effect cross-linking and grinding it to desired particle size for use. This resin will selectively and efficiently adsorb cesium ions in the presence of a high concentration of sodium ions with a low carbon to cesium ratio. 2 figs.

Cesium-specific phenolic ion exchange resin

DOEpatents

Bibler, Jane P.; Wallace, Richard M.

1995-01-01

A phenolic, cesium-specific, cation exchange resin is prepared by neutralizing resorcinol with potassium hydroxide, condensing/polymerizing the resulting intermediate with formaldehyde, heat-curing the resulting polymer to effect cross-linking and grinding it to desired particle size for use. This resin will selectively and efficiently adsorb cesium ions in the presence of a high concentration of sodium ions with a low carbon to cesium ratio.

Exchangeable Sodium Percentage decrease in saline sodic soil after Basic Oxygen Furnace Slag application in a lysimeter trial.

PubMed

Pistocchi, Chiara; Ragaglini, Giorgio; Colla, Valentina; Branca, Teresa Annunziata; Tozzini, Cristiano; Romaniello, Lea

2017-12-01

The Basic Oxygen Furnace Slag results from the conversion of hot metal into steel. Some properties of this slag, such as the high pH or calcium and magnesium content, makes it suitable for agricultural use as a soil amendment. Slag application to agricultural soils is allowed in some European countries, but to date there is no common regulation in the European Union. In Italy soils in coastal areas are often affected by excess sodium, which has several detrimental effects on the soil structure and crop production. In this study, carried out within an European project, the ability of the Basic Oxygen Furnace Slag to decrease the soil Exchangeable Sodium Percentage of a sodic soil was evaluated. A three-year lysimeter trial with wheat and tomato crops was carried out to assess the effects of two slag doses (D1, 3.5 g kg -1 year -1 and D, 2, 7 g kg -1 year -1 ) on exchangeable cations in comparison with unamended soil. In addition, the accumulation in the topsoil of vanadium and chromium, the two main trace metals present in the Basic Oxygen Furnace Slag, was assessed. After two years, the soil Exchangeable Sodium Percentage was reduced by 40% in D1 and 45% in D2 compared to the control. A concomitant increase in exchangeable bivalent cations (Ca ++ and Mg ++ ) was observed. We concluded that bivalent cations supplied with the slag competed with sodium for the sorption sites in the soil. The slag treatments also had a positive effect on tomato yields, which were higher than the control. Conversely the wheat yield was lower in the slag-amended soil, possibly because of the toxicity of vanadium added with the slag. This study showed that Basic Oxygen Furnace Slag decreased the Exchangeable Sodium Percentage, but precautions are needed to avoid the build up of toxic concentrations of trace metals in the soil, especially vanadium. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, characterization and application of ion exchange resin as a slow-release fertilizer for wheat cultivation in space

NASA Astrophysics Data System (ADS)

Li, Bowei; Dong, Chen; Chu, Zhengpei; Zhang, Weizhe; Wang, Minjuan; Liu, Hong; Xie, Beizhen

2016-10-01

In addition to the bio-regenerative air revitalization, water recycling and waste management systems and their associated challenges, enhancing the crop yield with less fertilizer input for sustainable food production in space is also a challenge that needs to be overcome. The purpose of this study is to investigate the feasibility of applying ion exchange resin as a slow-release fertilizer for wheat cultivation in space. Strong-acid cationic exchange resins and weak-base anion exchange resins soaked in 1X, 5X, 10X and 15X Hoagland nutrient solutions, respectively, were used as fertilizers in clinoptilolite to cultivate wheat plants, and the morphological and physiological characteristics of the wheat plants were studied and compared with that of the wheat planted in vermiculite and nutrient solutions. The results showed that more ions were attached on the surface of the ion exchange resins as the solution concentration increased. After 14 days, the fresh weight of wheat planted in the ion exchange resin-clinoptilolite (IER-clinoptilolite) treated with 10X and 15X solutions were 190% and 192% higher than that of wheat planted in nutrient solution with the same concentration. Chlorophyll content of wheat plants cultivated in the two kinds of solid medium is significantly higher than that of liquid cultivation. The lowest peroxidase (POD) activity and malondialdehyde (MDA) contents of wheat plants cultivated in the IER-clinoptilolite appeared on the 14th day. According to all the experimental data, it's promising to produce slow-release nutrient fertilizer by using strong-acid cationic exchange resins and weak-base anion exchange resins for wheat cultivation in space.

Empirical and mechanistic evaluation of NH4(+) release kinetic in calcareous soils.

PubMed

Ranjbar, F; Jalali, M

2014-05-01

Release, fixation, and distribution of ammonium (NH4(+)) as a source of nitrogen can play an important role in soil fertility and plant nutrition. In this study, ten surface soils, after addition of 1,000 mg NH4(+) kg(-1,) were incubated for 1 week at the field capacity moisture and 25 ± 2 °C temperature, and then NH4(+) release kinetic was investigated by sequential extractions with 10 mM CaCl2. Furthermore, NH4(+) distribution among three fractions, including water-soluble, exchangeable, and non-exchangeable, was determined in all soil samples. NH4(+) release was initially rapid followed by a slower reaction, and this was described well with the Elovich equation as an empirical model. The cumulative NH4(+) concentration released in spiked soil samples had a positive significant correlation with sand content and negative ones with pH, exchangeable Ca(2+)m and K(+), cation exchange capacity (CEC), equivalent calcium carbonate (ECC), and clay content. The cation exchange model in the PHREEQC program was successful in mechanistic simulation of the release trend of native and added NH4(+) in all control and spiked soil samples. The results of fractionation experiments showed that the non-exchangeable fraction in control and spiked soil samples was greater than that in water-soluble and exchangeable fractions. Soil properties, such as pH, exchangeable Ca(2+) and K(+), CEC, ECC, and contents of sand and clay, had significant influences on the distribution of NH4(+) among three measured fractions. This study indicated that both native and recently fixed NH4(+), added to soil through the application of fertilizers, were readily available for plant roots during 1 week after exposure.

Systematic interpolation method predicts protein chromatographic elution with salt gradients, pH gradients and combined salt/pH gradients.

PubMed

Creasy, Arch; Barker, Gregory; Carta, Giorgio

2017-03-01

A methodology is presented to predict protein elution behavior from an ion exchange column using both individual or combined pH and salt gradients based on high-throughput batch isotherm data. The buffer compositions are first optimized to generate linear pH gradients from pH 5.5 to 7 with defined concentrations of sodium chloride. Next, high-throughput batch isotherm data are collected for a monoclonal antibody on the cation exchange resin POROS XS over a range of protein concentrations, salt concentrations, and solution pH. Finally, a previously developed empirical interpolation (EI) method is extended to describe protein binding as a function of the protein and salt concentration and solution pH without using an explicit isotherm model. The interpolated isotherm data are then used with a lumped kinetic model to predict the protein elution behavior. Experimental results obtained for laboratory scale columns show excellent agreement with the predicted elution curves for both individual or combined pH and salt gradients at protein loads up to 45 mg/mL of column. Numerical studies show that the model predictions are robust as long as the isotherm data cover the range of mobile phase compositions where the protein actually elutes from the column. Copyright © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of various cations on the catalytic properties of clays. [polymerization of alanine adenylate

NASA Technical Reports Server (NTRS)

Paecht-Horowitz, M.

1978-01-01

The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

The influence of cation exchange treatment on the final characteristics of red wines.

PubMed

Lasanta, Cristina; Caro, Ildefonso; Pérez, Luis

2013-06-01

Ion exchange technology has been applied to adjust the pH of red wine and improve its tartaric and oxidative stability. Ion exchange appears to be a useful technique to achieve these objectives. Regarding the effect of ion exchange on organoleptic characteristics and the quality of the obtained wines, a slight decrease in both anthocyanin and tannin contents was observed along with a small drop in the aromatic content. However, the treated wines had lower hue and higher colour intensity and gave better punctuations in the sensory evaluation. These results confirm that ion exchange is an interesting technique for application in red winemaking. Copyright © 2012 Elsevier Ltd. All rights reserved.

Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion.

PubMed

Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

2016-05-01

A highly porous metal-organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2 (COO)4 ) and tetrameric (Zn4 (O)(CO2 )6 ), is successfully assembled by the reaction of a tricarboxylate ligand with Zn(II) ion. Subsequently, single-crystal-to-single-crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu(II) and Co(II) ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation-exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu(II) and Co(II) exchanged samples exhibit comparable CO2 adsorption capability to the pristine Zn(II) -based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that Zn(II) -based MOF affords the highest catalytic activity as compared with Cu(II) and Co(II) exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theory and applications of a novel ion exchange chromatographic technology using controlled pH gradients for separating proteins on anionic and cationic stationary phases.

PubMed

Tsonev, Latchezar I; Hirsh, Allen G

2008-07-25

pISep is a major new advance in low ionic strength ion exchange chromatography. It enables the formation of externally controlled pH gradients over the very broad pH range from 2 to 12. The gradients can be generated on either cationic or anionic exchangers over arbitrary pH ranges wherein the stationary phases remain totally charged. Associated pISep software makes possible the calculation of either linear, nonlinear or combined, multi-step, multi-slope pH gradients. These highly reproducible pH gradients, while separating proteins and glycoproteins in the order of their electrophoretic pIs, provide superior chromatographic resolution compared to salt. This paper also presents a statistical mechanical model for protein binding to ion exchange stationary phases enhancing the electrostatic interaction theory for the general dependence of retention factor k, on both salt and pH simultaneously. It is shown that the retention factors computed from short time isocratic salt elution data of a model protein can be used to accurately predict its salt elution concentration in varying slope salt elution gradients formed at varying isocratic pH as well as the pH at which it will be eluted from an anionic exchange column by a pISep pH gradient in the absence of salt.

Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

NASA Astrophysics Data System (ADS)

Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

Amino acid sequences of peptides from a chymotryptic digest of a urea-soluble protein fraction (U.S.3) from oxidized wool

PubMed Central

Corfield, M. C.; Fletcher, J. C.

1969-01-01

1. A chymotryptic digest of the protein fraction U.S.3. from oxidized wool was separated into 51 peptide fractions by chromatography on a column of cation-exchange resin. 2. The less acidic fractions were separated into their component peptides by a combination of cation-exchange-resin chromatography, paper chromatography and paper electrophoresis. 3. The amino acid sequences of 34 of these peptides were elucidated, and those of 14 others partially determined. 4. Overlaps between the tryptic and chymotryptic peptides from fraction U.S.3 have enabled ten extended amino acid sequences to be deduced, the longest containing 20 amino acid residues. 5. The relevance of the results to the structures of the helical and non-helical regions of wool is discussed. PMID:5395876

Application of cation-exchange solid-phase extraction for the analysis of amino alcohols from water and human plasma for verification of Chemical Weapons Convention.

PubMed

Kanaujia, Pankaj K; Tak, Vijay; Pardasani, Deepak; Gupta, A K; Dubey, D K

2008-03-28

The analysis of nitrogen containing amino alcohols, which are the precursors and degradation products of nitrogen mustards and nerve agent VX, constitutes an important aspect for verifying the compliance to the CWC (Chemical Weapons Convention). This work devotes on the development of solid-phase extraction method using silica- and polymer-based SCX (strong cation-exchange) and MCX (mixed-mode strong cation-exchange) cartridges for N,N-dialkylaminoethane-2-ols and alkyl N,N-diethanolamines, from water. The extracted analytes were analyzed by GC-MS (gas chromatography-mass spectrometry) in the full scan and selected ion monitoring modes. The extraction efficiencies of SCX and MCX cartridges were compared, and results revealed that SCX performed better. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 2 mL methanol containing 10% NH(4)OH and limits of detection could be achieved up to 5 x 10(-3) microg mL(-1) in the selected ion monitoring mode and 0.01 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of amino alcohol present in water sample sent by Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests. The method was also applied to extract the analytes from human plasma. The SCX cartridge showed good recoveries of amino alcohols from human plasma after protein precipitation.

Cation exchange concentraion of the Americium product from TRUEX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barney, G.S.; Cooper, T.D.; Fisher, F.D.

1991-06-01

A transuranic extraction (TRUEX) process has been developed to separate and recover plutonium, americium, and other transuranic (TRU) elements from acid wastes. The main objective of the process is to reduce the effluent to below the TRU limit for actinide concentrations (<100 nCi/g of material) so it can be disposed of inexpensively. The process yields a dilute nitric acid stream containing low concentrations of the extracted americium product. This solution also contains residual plutonium and trace amounts of iron. The americium will be absorbed into a cation exchange resin bed to concentrate it for disposal or for future use. Themore » overall objective of these laboratory tests was to determine the performance of the cation exchange process under expected conditions of the TRUEX process. Effects of acid, iron, and americium concentrations on americium absorption on the resin were determined. Distribution coefficients for americium absorption from acide solutions on the resin were measured using batch equilibrations. Batch equilibrations were also used to measure americium absorption in the presence of complexants. This data will be used to identify complexants and solution conditions that can be used to elute the americium from the columns. The rate of absorption was measured by passing solutions containing americium through small columns of resin, varying the flowrates, and measuring the concentrations of americium in the effluent. The rate data will be used to estimate the minimum bed size of the columns required to concentrate the americium product. 11 refs. , 10 figs., 2 tabs.« less

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

PubMed

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.