Divalent Cation Species Research Articles

An experimental study of the alteration of basalt on the surface of Venus

Characterizing the surface of Venus has been complicated by its thick atmosphere and caustic surface conditions (~470 °C, 90 bars). Several approaches, including the collection of spectral data, thermodynamic modelling, lander missions, and surface weathering laboratory experiments have progressed our view of what lies at the surface. However, surface-atmosphere interactions remain somewhat unconstrained and interpretations of the spectral data rely on an understanding of the surface-atmosphere alteration. We used a cold-seal pressure vessel apparatus pressurized with pure CO2 gas and both synthetic and natural glassy basalts specimens to simulate chemical weathering on the surface of Venus for a duration of two weeks. The extent of alteration was described from the surface of samples to depth using Rutherford Backscatter Spectroscopy (RBS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. We describe the alteration zones of reacted basalt specimens and report an enrichment of divalent cation species at the near surfaces of basalts; Ca2+ was enriched by ~5 wt% and Fe2+ was enriched by ~1–2 wt%. The enrichment at the near surface favors the production of iron (Fe) oxide(s) and carbonates on the surfaces, which form discontinuous coatings on all reacted samples in two weeks duration. Our results aid in the interpretation of radar emissivity data by constraining which alteration products should be present on the surface and suggesting timeframes necessary for their detection. Assuming that radar emissivity is able to discern weathered basalt, especially those dominated by carbonates and/or semiconducting minerals Fe oxide(s), our results suggest that basalts at Idunn Mons in Imdr Regio previously thought to be anywhere from 2.5 million to a few years old (Smrekar et al., 2010; D'Incecco et al., 2017; Filiberto et al., 2020; Cutler et al., 2020) could instead be as young as 65,000 years to 110,000 years depending on basalt type.

Lattice Boltzmann method to simulate three-dimensional ion channel flow using fourth order Poisson–Nernst–Planck–Bikerman model

Over the past three decades, the lattice Boltzmann method (LBM) has been applied to a vast range of hydrodynamic and non-hydrodynamic (e.g., ion transport) systems. In conjunction with the immersed boundary method (IBM), the LBM has been successfully implemented to solve systems with complex geometries. In this study, the immersed boundary–lattice Boltzmann method (IB-LBM) is implemented to simulate nanoscale ion transport. Traditionally, ion transport is described through the Poisson–Nernst–Planck (PNP) equations where ionic interactions are included. In the current paper, the fourth order Poisson–Nernst–Planck–Bikerman (4PNPBik) model has been used. In addition to ionic interactions, the 4PNPBik model includes the effects of the finite size of particles (ions and water) and interactions between ions and its surrounding medium. Applicability of the 4PNPBik model is demonstrated through comparison of the experimental and predicted ion activity. Implementation of the 4PNPBik model has been validated by comparing the predicted current–voltage curve with the analytical result. The transient receptor potential (TRP) ion channel of the vanilloid group (TRPV4) is used to demonstrate the applicability of this approach. The TRPV4 is a nonselective cation channel that prefers divalent cationic species over monovalent cations. In this study, this selectivity is demonstrated by comparing the concentration profiles of calcium, sodium, and chloride ions. Further, the role of the finite size of particles and nonlocal electrostatics is discussed by comparing the results obtained from the PNP and 4PNPBik models under identical initial and boundary conditions.

Self-assembly of highly ordered DNA origami lattices at solid-liquid interfaces by controlling cation binding and exchange

The surface-assisted hierarchical self-assembly of DNA origami lattices represents a versatile and straightforward method for the organization of functional nanoscale objects such as proteins and nanoparticles. Here, we demonstrate that controlling the binding and exchange of different monovalent and divalent cation species at the DNA-mica interface enables the self-assembly of highly ordered DNA origami lattices on mica surfaces. The development of lattice quality and order is quantified by a detailed topological analysis of high-speed atomic force microscopy (HS-AFM) images. We find that lattice formation and quality strongly depend on the monovalent cation species. Na+ is more effective than Li+ and K+ in facilitating the assembly of high-quality DNA origami lattices, because it is replacing the divalent cations at their binding sites in the DNA backbone more efficiently. With regard to divalent cations, Ca2+ can be displaced more easily from the backbone phosphates than Mg2+ and is thus superior in guiding lattice assembly. By independently adjusting incubation time, DNA origami concentration, and cation species, we thus obtain a highly ordered DNA origami lattice with an unprecedented normalized correlation length of 8.2. Beyond the correlation length, we use computer vision algorithms to compute the time course of different topological observables that, overall, demonstrate that replacing MgCl2 by CaCl2 enables the synthesis of DNA origami lattices with drastically increased lattice order.

The absorption and fluorescence spectra of 4-(3-methoxybenzylidene)-2-methyl-oxazalone interpreted by Franck-Condon simulation in various pH solvent environments.

The absorption and fluorescence spectra of 4-(3-methoxybenzylidene)-2-methyl-oxazalone (m-MeOBDI) dissolved in neutral, acidic, and basic solvent environments have been investigated and assigned by using Franck-Condon (FC) simulations at the quantum TDDFT level. Four different structures of m-MeOBDI in the ground and excited states are optimized and are found to be responsible for the observed absorption and fluorescence spectra. The (absorption) fluorescence of m-MeOBDI in pure methanol and neutral/basic methanol/water (1/9 vol) mixed solvent is found to arise from the (ground neutral N-I) excited neutral N-I* and cationic C-III* species, respectively. In acidic solvent, the absorption is found to arise from ground acidic C-II species, and the excited divalent cation DC-IV* is found to be formed in its excited state due to the excess H+ in the solution, and then it emits ∼560 nm fluorescence. FC simulations have also been employed to confirm our assignments as well as interpret the vibronic band profiles. As expected, the simulated emission spectrum of the divalent cationic species is in good agreement with the experimental observation. Therefore, within the present FC simulation, the observed absorption and fluorescence spectra have been reasonably interpreted and novel fluorescence mechanisms of m-MeOBDI in various pH solvent environments have been proposed.

Unprecedentedly High Activity and/or High Regio-/Stereoselectivity of Fluorenyl-Based CGC Allyl-Type η3:η1-tert-Butyl(dimethylfluorenylsilyl)amido Ligated Rare Earth Metal Monoalkyl Complexes in Olefin Polymerization.

A series of fluorenyl-based constrained-geometry-configuration (CGC) allyl-type rare earth metal monoalkyl complexes bearing the divalent anionic η3:η1-tert-butyl(dimethylfluorenylsilyl)amido (η3:η1-FluSiMe2NtBu) ligand (η3:η1-FluSiMe2NtBu)Ln(CH2SiMe3)(THF)2 (1–3) have been synthesized via the alkane elimination reaction between the FluHSiMe2NHtBu ligand and rare earth metal tri(trimethylsilylmethyl) complexes Ln(CH2SiMe3)3(THF)n. Their structures are characterized by means of NMR spectrum, elemental analyses, and X-ray diffraction. These complexes 1–3 are isostructural and isomorphous, and each of them adopts a distorted-trigonal-bipyramidal configuration containing one η3:η1-FluSiMe2NtBu ligand, one CH2SiMe3 ligand, and two THF molecules. Unlike traditional CGC allyl-type rare earth metal complexes showing no or low activity and regio-/stereoselectivity in styrene or MMA polymerization, these complexes 1–3 exhibit high catalytic activities and/or high regio-/stereoselectivities in the cis-1,4-polymerization of isoprene and myrcene or in the syndiotactic polymerization of styrene under the aid of different activators (borate or borane) and AlR3. The in situ 1H NMR spectra suggest that the exchanges of chelating ligands such as alkyl groups and divalent anionic η3:η1-FluSiMe2NtBu ligands between rare earth metal centers and Al centers result in the formation of a heterobimetallic tetraalkylaluminate complex R2Al(μ-R)2Ln(R)(μ-R)2AlR2, which is activated by activators to form a divalent cationic species [Ln(μ-R)2AlR2]2+ as a catalytically active species in the coordination–insertion polymerization of olefins.

Synthesis and characterization of divalent ion conductors with NASICON-type structures

ABSTRACTDivalent ion-conducting solid electrolytes with NASICON-type three-dimensional network structures (MxHf1−x)4/(4−2x)Nb(PO4)3 (M = Ni, Mg, Ca, Sr) were successfully developed by introducing M2+ cations into HfNb(PO4)3 solids. The presence of high-valence cations such as Hf4+, Nb5+, and P5+ in the structures effectively reduced the electrostatic interaction between the conducting M2+ cations and the surrounding oxide anions, enabling the M2+ cations to migrate smoothly in the rigid crystal lattice. The relationship between the cation conductivity in NASICON-type solids and the ionic radius of the migrating divalent cation species was also clarified by taking into account the relative sizes of the conduction pathways in the structures.

The recyclability of alginate hydrogel particles used as a palladium catalyst support

We investigated the catalytic efficiency of alginate hydrogels used as a catalyst support. An alginate solution containing palladium and magnetic nanoparticles was dropped continuously through a tapered glass capillary using a syringe pump, and the generated alginate droplets were collected in an aqueous solution containing divalent cations. The prepared PdNPs/MNPs-embedded alginate particles were used as a catalyst, catalyst support, and magnetic stirrer for the reduction of 4-nitrophenol. The catalytic reactions were found to depend on the magnetic stirring of the alginate hydrogels. Furthermore, we examined the recyclability while changing the alginate concentration, divalent cation species, and incubation protocols.

Identifying the Metal That Activates the Prenyltransferase That Catalyzes Formation of Geranyl Diphosphate in the Diatom Pseudo‐nitzschia multiseries

Domoic acid (DA) is a neurotoxin synthesized by marine diatoms of the genus Pseudo‐nitzschia which causes amnesiac shellfish poisoning in humans and death of marine wildlife. Geranyl diphosphate (GPP), a key intermediate in domoic acid biosynthesis, is formed from the “head‐to‐tail” condensation of isopentenyl diphosphate and dimethylallyl diphosphate in a reaction catalyzed by a member of the prenyltransferase family of enzymes. These prenyltransferases can generate different chain‐length products, including geranyl diphosphate (C10), farnesyl diphosphate (FPP, C15), and geranylgeranyl diphosphate (GGPP, C20), all of which are precursors to terpenoid natural products. Prenyltransferases require a divalent metal cation for activity. Previous work has shown that a single prenyltransferase can generate multiple products (GPP, FPP, and GGPP), and that the product distribution will vary depending on the species of divalent cation used to support the reaction (Mg2+, Mn2+, or Co2+). Here, we measured the levels of Mg2+, Mn2+, and Co2+ in Pseudo‐nitzschia cells to determine which ion is most likely to support GPP formation. Three samples of Pseudo‐nitzschia multiseries cultured in sea water were harvested by centrifugation. Samples were digested with HNO3 before analysis using atomic absorption spectroscopy. The average concentration of Mg2+ present, per cell and per μm3, is over 100‐fold higher than the concentrations of Mn2+ and Co2+. This is consistent with results from studies in other systems, suggesting that Mg2+ is the main cofactor that activates the prenyltransferase that generates GPP for domoic acid biosynthesis in Pseudo‐nitzschia.Support or Funding InformationThis project is supported by the SURE (Summer Undergraduate Research Experience) Award Program from the College of Natural Science and Mathematics, California State University Sacramento.

Characterization of tRNALeu binding interactions with Cu2 + and Pb2 + and their biological implications

RNA is known to interact with Mg2+ when assuming higher-ordered tertiary configurations. Structurally, when tRNA molecules interact with Mg2+, they consistently form a “L-shape” conformation each time they are synthesized. Therefore, if Mg2+ can induce tertiary structure formation, then binding to alternative cations could produce alternative tertiary configurations. By utilizing circular dichroism and mobility gel-shift assays it was observed that tRNA structure can be altered when in the presence of different divalent cationic species. Formation of these alternative structural configurations was further validated by aminoacylating these tRNA structural anomalies with their native enzyme, which resulted in markedly different degrees of activity. Thus, it was confirmed that structural changes do occur when tRNA forms complexes with different cations. To better understand these structural changes, quantitative cation binding to tRNA was determined through titrations as well as ICP-OES analysis, which indicated that the metal ions can bind to the tRNA structure in specific and non-specific ways. Lastly, it was observed through stopped-flow kinetics that tRNA can associate/dissociate from different cations to varying degrees, thus forming cation-specific complexes at unique rates.

The Isotope Geochemistry of Ni

Nickel is an iron-peak element with 5 stable isotopes (see Table 1) which is both cosmochemically abundant and rich in the information carried in its isotopic signature. Significantly, 60Ni is the radiogenic daughter of 60Fe, a short-lived nuclide (t1/2 = 2.62 Ma; Rugel et al. 2009) of a major element. 60Fe has the potential to be both an important heat source and chronometer in the early solar system. 60Ni abundances serve to document the prior importance 60Fe and this is a topic of on-going debate (see Extinct 60 Fe and radiogenic 60 Ni ). The four other stable Ni nuclides span a sizeable relative mass range of ~10%, including the notably neutron-rich nuclide 64Ni. The relative abundances of these isotopes vary with diverse stellar formation environments and provide a valuable record of the nucleosynthetic heritage of Ni in the solar system (see Nucleosynthetic Ni isotopic variations ). Ni occurs widely as both elemental and divalent cationic species, substituting for Fe and Mg in common silicate structures and forming Fe/Ni metal alloys. The Ni isotope chemistry of all the major planetary reservoirs and fractionations between them can thus be characterized (see Mass-Dependent Ni isotopic Variability ). Ni is also a bio-essential element and its fractionation during low-temperature biogeochemical cycling is a topic that has attracted recent attention (see Mass-Dependent Ni isotopic Variability ). ### Notation Much of the work into Ni has been cosmochemical, focussing on the nucleosynthetic origins of different meteoritic components. Such studies have primarily investigated mass-independent isotopic variations, both radiogenic and non-radiogenic, which require choosing a reference isotope pair for normalization. Throughout this work we use 58Ni–61Ni as the normalizing pair, in keeping with current practice in the field. An alternative 58Ni–62Ni normalization scheme has previously been used for bulk …

Design Principles of DNA Enzyme-Based Walkers: Translocation Kinetics and Photoregulation.

Dynamic DNA enzyme-based walkers complete their stepwise movements along the prescribed track through a series of reactions, including hybridization, enzymatic cleavage, and strand displacement; however, their overall translocation kinetics is not well understood. Here, we perform mechanistic studies to elucidate several key parameters that govern the kinetics and processivity of DNA enzyme-based walkers. These parameters include DNA enzyme core type and structure, upper and lower recognition arm lengths, and divalent metal cation species and concentration. A theoretical model is developed within the framework of single-molecule kinetics to describe overall translocation kinetics as well as each reaction step. A better understanding of kinetics and design parameters enables us to demonstrate a walker movement near 5 μm at an average speed of ∼1 nm s(-1). We also show that the translocation kinetics of DNA walkers can be effectively controlled by external light stimuli using photoisomerizable azobenzene moieties. A 2-fold increase in the cleavage reaction is observed when the hairpin stems of enzyme catalytic cores are open under UV irradiation. This study provides general design guidelines to construct highly processive, autonomous DNA walker systems and to regulate their translocation kinetics, which would facilitate the development of functional DNA walkers.

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

Gismondine (P) ion exchanged with Cu2+, Zn2+, and Ni2+ were used as solid supports for the immobilization of the lipase Rhizomucor miehei enzyme. Physicochemical characterization of the zeolite–enzyme complexes were performed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and attenuated total reflectance–Fourier transform infrared (ATR–FTIR). These biocatalysts were used for the transesterification reaction of soybean oil to biodiesel. Divalent cation species and thermal treatment of the zeolitic supports had different effects on several parameters under investigation. In terms of the enzyme activity, the zeolite–enzyme complexes prepared with Ni-P were superior in comparison to the other ones and a synergistic effect for the zeolite–enzyme complex (Ni-P/200-ENZ) was observed for the transesterification reactions of soybean oil to biodiesel. The total amount of methyl esters produced by the complex Ni-P/200-ENZ was of 56.2%, while the same concentration of the immobilized enzyme in its free form yielded only 39.3% of methyl esters, and Ni-P/200 in its pure form also yielded a very low amount of methyl esters (20%). The other zeolite–enzyme complexes (Zn-P/200-ENZ, Cu-P/200-ENZ, and Na-P/200-ENZ) presented a completely different behavior in comparison to the Ni-P/200-ENZ complexes. The total yields of methyl esters generated by these biocatalysts were very low and no synergistic effects were observed. A correlation between the cation atomic radius and the enzymatic activity of the zeolite–enzyme complexes was observed. It was noticed that the bigger the atomic radius of the extra-framework cation, smaller was the experimental enzymatic activity coefficient.

Influence of Cationic Composition and pH on the Formation of Metal Stearates at Oil–Water Interfaces

We study the formation of layers of metal stearates at the interface between a decane solution of stearic acid and aqueous salt solutions of variable composition and pH by monitoring the evolution of their mechanical, optical, and chemical properties as a function of time after formation of the interface. For values of the pH below the pK(a) of stearic acid hardly any interfacial activity is observed. For pH > pK(a), stearic acid deprotonates at the interface and forms metal stearates, eventually leading to the formation of macroscopic solid layers. Dynamic interfacial tension measurements reveal that the process takes place in several stages, which we attribute to the successive formation of dilute and dense monolayers followed by three-dimensional growth. In the presence of divalent ions, the solid layers display a significant increase in the dilatational storage modulus. Experiments performed with an aqueous phase containing multiple cation species (artificial seawater) give rise to particularly pronounced growth of solid layers, which preferentially incorporate Ca(2+) as revealed by X-ray photoelectron and infrared spectroscopy. Our results highlight in particular the importance of the complex synergistic effects of simultaneously present monovalent and divalent cation species on the interfacial adsorption.

Biomimetic Underwater Adhesives with Environmentally Triggered Setting Mechanisms

The challenges of developing medical adhesives for the wet environment of open surgery are analogous to the adhesion problems solved by marine organisms living at the watery interface of land and ocean. These organisms routinely bond dissimilar materials together under seawater with little if any surface preparation. One such organism is the sandcastle worm (Phragmatopoma californica). Our goal is to copy this marine worm’s mechanisms of underwater bonding to create synthetic water-borne underwater medical adhesives, and in turn, to use the synthetic adhesives to test mechanistic hypotheses about the natural adhesive. Biomimetic underwater adhesives were formulated with polyelectrolytic analogues of the natural glue proteins. The copolymers condensed into complex coacervates—dense partially water-immiscible cohesive fluids poised between soluble polymers and insoluble polymeric salts. The boundary between fluid coacervate phases and solid or gelled states was dependent on divalent cation species as well as the pH and temperature, which demonstrated that these environmental factors can trigger the adhesive setting reaction (Fig. 1). The results provide, respectively, empirical support for the natural pH-triggered set hypothesis and practical triggers for controlled setting of mimetic medical adhesives.

An Examination of the Influence of Divalent Cationic Dopants on the Bulk and Surface Properties of Ba(NO3)2 Associated with Crystallization

The incorporation of divalent cationic species associated with the crystallization of Ba(NO3)2 related to nuclear waste storage issues is studied via the development and exploitation of a versatile and transferable empirical atom−atom forcefield for both mono- and divalent nitrates. Studies of binary and tertiary systems using Mott−Littleton and bulk supercell defect calculations reveals Ca2+ ions to be the most energetically favored species for incorporation into the Ba(NO3)2 lattice over Sr2+ and Pb2+ ions. Incorporation modeling also confirms solid−solution behavior with an excellent Vegard’s Law fit. Tertiary systems involving Ba2+, Ca2+, and Sr2+ ions are found to become less stable with increasing concentrations, notably of Sr2+. Morphological predictions using attachment and surface energy methods reveal a well-defined cube-octahedron habit, with negligible differences between Ba(NO3)2 and Sr(NO3)2. Surface relaxation effects are found to be very small, with no apparent impact on the predicted crystal morphology, consistent with a very stable surface structure, reflecting both the close packing nature of the {100} and {111} habit faces and the strong in-plane Coulombic interactions between the cations and the anions. Examination of Sr2+ incorporation onto Ba(NO3)2 crystal habit surfaces is in good agreement with experimental observations of the crystal morphology revealing preferential incorporation onto the {111}surfaces, with respect to the {100} surfaces, where the former case displays a layerlike packing of cations and anions that more easily effects the impurity incorporation process and hence prevents further growth, resulting in a more octahedral morphology.

Dynamic change in the distribution of alpha5beta1 integrin on isolated ventral membrane: effect of divalent cation species.

We investigated the spatial distribution of alpha5beta1 integrin in isolated ventral plasma membranes (VPMs) of human foreskin fibroblasts in order to elucidate how the interaction of integrin with cytoskeletal and extracellular matrix proteins might affect the integrin distribution. Cells were exposed to the jet of buffer to remove the apical surface and most of cellular organelles. After this treatment VPMs, which adhered to the glass surface, possessed the cellular structures such as fibronectin (FN) fibrils and actin stress fibers. The isolated VPMs thus prepared were employed without fixation to investigate the change in the integrin distribution. In isolated VPMs, alpha5beta1 integrin, labeled with Cy3-tagged anti-integrin antibody, was found to accumulate not only at the tips of stress fibers but also along FN fibrils extending from there. When divalent cations were removed with EDTA, the accumulated integrin was dispersed, and the original pattern of distribution was recovered upon restoration of divalent cations. Talin, an integrin-actin cytoskeleton linker protein, was found to accumulate only at the tips of stress fibers in isolated VPMs, but alpha5beta1 integrin did not exhibit strong accumulation there, indicating that talin played little role in integrin distribution in isolated VPMs. The amount of alpha-actinin associated with stress fibers was found to drastically decrease in isolated VPMs, which was presumably related to the failure of localization of integrin at the tips of stress fibers. It was also shown that the association of stress fibers to isolated VPMs seemed to be independent of accumulation of integrin.

Inhibitory action of diltiazem on voltage-gated calcium channels in cone photoreceptors

The benzothiazepine, diltiazem, is commonly used as an inhibitor of vascular L-type Ca channels, and is a clinically important anti-anginal and antihypertensive medication. In the retina, diltiazem also inhibits cyclic-nucleotide gated (CNG) channels, including the cGMP-gated channels in photoreceptors, and has been suggested to be a neuroprotectant in an animal model of retinitis pigmentosa, a degenerative disease of photoreceptors. In contrast to CNG channels, the actions of diltiazem on photoreceptor Ca channels have not been studied. We show that d- cis-diltiazem can block Ca channels in cone photoreceptors and that the potency and efficacy of cone photoreceptor Ca channel inhibition by this drug is unconventional. Over the concentration range of 5–500 μ m diltiazem, the dose response curve was biphasic with a high affinity saturation level of ∼30% block in the 20–50 μ m range (IC 50=4·9 μ m) and a low affinity saturation block (near 100%) with concentrations up to 500 μ m (IC 50=100·4 μ m). The degree of block was found to be equivalent when Bay K 8644 was used to increase Ca channel current, indicating that the levels of block do not result from multiple Ca channel subtypes having differing sensitivities to diltiazem. Calcium imaging showed that the relatively low efficacy of the high-affinity Ca channel block was not due to the species of charge-carrying divalent cation nor that it was associated with dialysis of cellular contents. These data contribute to an emerging perspective that the photoreceptor Ca channel has properties unique from other L-type channels, an important consideration should these channels become a target for testing putative neuroprotective therapies.

Acidity and 1-butene isomerization of synthesized smectite-type catalysts containing different divalent cations

Smectite-type materials which contain different divalent cations (Ni 2+, Co 2+, Mg 2+, and Zn 2+) in octahedral sheets have been synthesized and characterized by pyridine adsorption and catalytic effectiveness for the isomerization of 1-butene. All smectite-type materials examined have Lewis acid sites; however, the activity values for the isomerization of 1-butene significantly depend on the divalent cation species included. Nickel-containing smectite-type catalysts are stable and the most active among the smectite catalysts.

Use of Soil Amendments to Reduce Nitrogen, Phosphorus and Heavy Metal Availability

The primary objectives of this study were to determine (1) the exchange characteristics of various soil amendments using a range of salt solutions, (2) the effect of selected soil amendments on heavy metal (Cu2+, Pb2+, and Zn2+) availability, and (3) the effect of selected soil amendments on NH4 + and P availability. The CEC of zeolite and red mud obtained using solutions of 0.1 M BaCl2 and 0.1 M BaCl2/NH4Cl were significantly lower than values obtained using 1 M KCl and 1 M NH4Cl. The higher CEC obtained with monovalent cations indicated that larger divalent cations could not enter the mineralogical framework of zeolite and red mud, and, consequently, a number of exchange sites were only accessible to the smaller monovalent cations. These findings suggest that 1 M KCl and 1 M NH4NO3 should be used as the extracting solutions to obtain the best estimation of CEC and ECEC of red mud and zeolite. The ability of red mud, zeolite, and calcium phosphate (Ca-P), mixed at rates of 0%, 5%, 10%, and 20% (w/w), to sorb Cu2+, Pb2+, and Zn2+ generally followed the order: red mud>zeolite>>Ca-P, while the affinity sequence for these metals followed the order: Pb2+≥Cu2+>>Zn2+. The higher affinity of the sand/amendment mixtures for Pb2+ and Cu2+ relative to Zn2+ was attributed to metal hydrolysis and subsequent specific adsorption as Pb(OH)+ and Cu(OH)+. Zinc was considered to have been primarily sorbed as the divalent cation species. Rates of 5% (w/w) adequately reduced the availability of heavy metals to concentrations below environmental guidelines based on the Toxicity Characteristic Leaching Procedure. Red mud and zeolite added at a rate of 10% (w/w) to the A and B horizon of a sandy soil significantly increased their ability to remove NH4 + from solution, but had negligible effect on P sorption compared with unamended soils. Increased NH4 + removal was attributed to the associated increase in CEC and the greater selectivity of the exchange sites for this cation relative to resident exchangeable Ca2+ and Na+. The absence of P sorption by these two amendments was attributed to the high pH and predominantly negative surface charge of the red mud and the lack of sorption sites in zeolite. Gypsum, on the other hand, tended to depress NH4 + retention but markedly increased P sorption. The depressive effect on NH4 + was due to increased competition between NH4 + and Ca2 + for a limited number of exchange sites, while formation of calcium phosphates of low solubility was the possible mechanism for increased P sorption.

Effects of divalent cations on exocytosis and endocytosis from single mouse pancreatic beta‐cells.

1. The effects of the divalent cations Ca2+, Ba2+ and Sr2+ on exocytosis and endocytosis from single isolated mouse pancreatic beta-cells were investigated by monitoring changes in cell capacitance. 2. The immediate increase in capacitance elicited by a single depolarization from -70 to +20 mV was dependent on the divalent cation species, with Ca2+ (8.2 +/- 1.1 fF pC-1) > Ba2+ (1.0 +/- 0.2 fF pC-1) > Sr2+ (0.7 +/- 0.2 fF pC-1) in perforated-patch recordings. 3. In Ba2+ solutions alone there was subsequently an additional slow increase in capacitance (to 4.3 +/- 1.1 fF pC-1). This second phase of exocytosis was unaffected by preincubation with colcemid (20 microM, 45 min) or cytochalasin D (10 microM, 15 min), suggesting that interaction of secretory granules with microtubules or microfilaments is not involved. 4. An increase in cell capacitance was elicited by depolarization in Ba2+ solutions when intracellular Ca2+ was buffered with 10 mM EGTA. Infusion of the beta-cell with Ba2+ also stimulated exocytosis although the rate was much slower (1.1 +/- 0.2 fF s-1; 8 microM free Ba2+) than for Ca2+ (39 +/- 5 fF s-1; 2 microM free Ca2+). These data indicate that Ba2+ does not evoke secretion by promoting Ca2+ release from internal stores. 5. The lower efficacy of Ba2+ in supporting exocytosis may be related to the fact that this cation does not activate calmodulin-dependent processes and the slow second phase of secretion may result from this ion being removed only slowly from the cytoplasm. 6. Endocytosis was faster in Sr2+ than in Ca2+ or Ba2+ solution, and the speed increased when the external concentration of all three divalent cation species was raised. The ability of Ba2+ to support endocytosis suggests calmodulin-dependent processes are not involved. These data suggest membrane retrieval is regulated differently from exocytosis in beta-cells.